Atmospheric corrosion of zinc-aluminum and

copper-based alloys in chloride-rich environments

Microstructure, corrosion initiation, patina evolution

and metal release
 

Xian Zhang

Doctoral Thesis
Stockholm, Sweden 2014

 
 
Akademisk avhandling som med tillstånd av Kungliga Tekniska Högskolan framlägges till
offentlig granskning for avläggande av teknologie doktorsexamen fredagen den 26 september
2014 klockan 10:00 i Kollegiesalen, Kungliga Tekniska Högskolan, Brinellvägen 8,
Stockholm. Avhandlingen presenteras på engelska.

Atmospheric corrosion of zinc-aluminum and copper-based alloys in chloride-rich

environments.
-Microstructure, corrosion initiation, patina evolution and metal release.

Xian Zhang (xianzh@kth.se)

Doctoral Thesis

KTH Royal Institute of Technology

School of Chemical Science and Engineering
Department of Chemistry
Division of Surface and Corrosion Science
Drottning Kristinas väg 51
SE-100 44 Stockholm, Sweden

TRITA-CHE Report 2014:27

ISSN 1654-1081
ISBN 978-91-7595-203-1

Denna avhandling är skyddad enligt upphovsrättslagen. Alla rättigheter förbehålles.

Copyright © 2014 Xian Zhang. All rights reserved. No part of this thesis may be reproduced
by any means without permission from the author.

The following items are printed with permission:

PAPER I: © 2012 Elsevier
PAPER II: © 2013 Elsevier
PAPER III: © 2013 Elsevier
PAPER IV: © 2014 Elsevier
PAPER V: © 2014 Elsevier

Printed at Universitetsservice US-AB

 

Make things as simple as possible,

but not simpler.

Albert Einstein

 
 
 

 
 
Abstract

Fundamental understanding of atmospheric corrosion mechanisms requires an in-

depth understanding on the dynamic interaction between corrosive constituents and
metal/alloy surfaces. This doctoral study comprises field and laboratory investigations
that assess atmospheric corrosion and metal release processes for two different groups
of alloys exposed in chloride-rich environments. These groups comprise two
commercial Zn-Al alloy coatings on steel, Galfan™ (Zn5Al) and Galvalume™
(Zn55Al), and four copper-based alloys (Cu4Sn, Cu15Zn, Cu40Zn and Cu5Zn5Al).
In-depth laboratory investigations were conducted to assess the role of chloride
deposition and alloy microstructure on the initial corrosion mechanisms and
subsequent corrosion product formation. Comparisons were made with long-term
field exposures at unsheltered marine conditions in Brest, France.
A multitude of surface sensitive and non-destructive analytical methods were
adopted for detailed in-situ and ex-situ analysis to assess corrosion product evolution
scenarios for the Zn-Al and the Cu-based alloys. Scanning electron microscopy and
energy dispersive spectroscopy (SEM/EDS) were employed for morphological
investigations and scanning Kelvin probe force microscopy (SKPFM) for nobility
distribution measurements and to gain microstructural information. SEM/EDS,
infrared reflection-absorption spectroscopy (IRAS), confocal Raman micro-
spectroscopy (CRM) and grazing incidence x-ray diffraction (GIXRD) were utilized
to gain information on corrosion product formation and possibly their lateral
distribution upon field and laboratory exposures. The multi-analytical approach
enabled the exploration of the interplay between the microstructure and corrosion
initiation and corrosion product evolution.
A clear influence of the microstructure on the initial corrosion product formation
was preferentially observed in the zinc-rich phase for both the Zn-Al and the Cu-Zn
alloys, processes being triggered by microgalvanic effects. Similar corrosion products
were identified upon laboratory exposures with chlorides for both the Zn-Al and the
Cu-based alloys as observed after short and long term marine exposures at field
conditions. For the Zn-Al alloys the sequence includes the initial formation of ZnO,
ZnAl2O4 and/or Al2O3 and subsequent formation of Zn6Al2(OH)16CO3·4H2O, and
Zn2Al(OH)6Cl·2H2O and/or Zn5(OH)8Cl2·H2O. The patina of Cu sheet consists of two
main layers with Cu2O predominating in the inner layer and Cu2(OH)3Cl in the outer
layer, and with a discontinuous presence of CuCl in-between. Additional patina
constituents of the Cu-based alloys include SnO2, Zn5(OH)6(CO3)2,

i
 
Zn6Al2(OH)16CO3·4H2O and Al2O3. General scenarios for the evolution of corrosion
products are proposed as well as a corrosion product flaking mechanism for some of
the Cu-based alloys upon exposure in chloride-rich atmospheres.
The tendency for corrosion product flaking was considerably more pronounced on
Cu sheet and Cu4Sn compared with Cu15Zn and Cu5Al5Zn. This difference is
explained by the initial formation of zinc- and zinc-aluminum hydroxycarbonates
Zn5(OH)6(CO3)2 and Zn6Al2(OH)16CO3·4H2O on Cu15Zn and Cu5Al5Zn, corrosion
products that delay the formation of CuCl, a precursor of Cu2(OH)3Cl. As a result, the
observed volume expansion during transformation of CuCl to Cu2(OH)3Cl, and the
concomitant flaking process of corrosion products, was less severe on Cu15Zn and
Cu5Al5Zn compared with Cu and Cu4Sn in chloride-rich environments. The results
confirm the barrier effect of poorly soluble zinc and zinc-aluminum
hydroxycarbonates Zn5(OH)6(CO3)2 and Zn6Al2(OH)16CO3·4H2O, which results in a
reduced interaction between chlorides and surfaces of Cu-based alloys, and thereby
reduced formation rates of easily flaked off corrosion products. From this process also
follows reduced metal release rates from the Zn-Al alloys.

Keywords: atmospheric corrosion, chloride deposition, Zn-Al alloy coatings on steel,

Cu sheet and Cu alloys, microstructure, corrosion initiation, corrosion product
evolution, metal release, SEM, IRAS, CRM.

ii
Sammanfattning

Bättre molekylär förståelse för metallers atmosfäriska korrosion kräver en

fördjupad kunskap i det dynamiska samspelet mellan atmosfärens korrosiva
beståndsdelar och metallytan. Denna doktorsavhandling omfattar laboratorie- och
fältundersökningar av korrosions- och metallfrigöringsprocesser av två grupper av
legeringar som exponerats i kloridrika atmosfärsmiljöer: två kommersiella Zn-Al
beläggningar på stål, Galfan™ (Zn med 5% Al, förkortat Zn5Al) och Galvalume™
(Zn55Al), samt fyra kopparbaserade legeringar (Cu4Sn, Cu15Zn, Cu40Zn och
Cu5Zn5Al). Undersökningar har genomförts i renodlade laboratorie-miljöer med för-
deponerade NaCl-partiklar i en atmosfär av varierande relativ fuktighet. Syftet har
varit att utvärdera betydelsen av kloriders deposition och legeringarnas mikrostruktur
på korrosionsmekanismen samt bildandet av korrosionsprodukter. Jämförelser av
korrosionsmekanismer har även gjorts efter flerårsexponeringar av samma legeringar
i en marin fältmiljö i Brest, Frankrike.
Undersökningarna har baserats på ett brett spektrum av analysmetoder för
detaljerade studier dels under pågående atmosfärisk korrosion (in-situ), och dels efter
avslutad korrosion (ex-situ). Legeringarnas mikrostruktur och tillhörande variation i
ädelhet hos olika faser har undersökts med svepelektronmikroskopi och
energidispersiv röntgenmikroanalys (SEM/EDS) samt med en variant av
atomkraftsmikroskopi (engelska: scanning Kelvin probe force microscopy, SKPFM).
Korrosionsprodukternas tillväxt har analyserats in-situ med infraröd reflektions-
absorptionsspektroskopi (IRAS), samt morfologi och sammansättning av bildade
korrosionsprodukter ex-situ med SEM/EDS, konfokal Raman mikro-spektroskopi
(CRM) samt röntgendiffraktion vid strykande ifall (GIXRD). Det multi-analytiska
tillvägagångssättet har medfört att det komplexa samspelet mellan de skilda
legeringarnas mikrostruktur, korrosionsinitiering och bildandet av
korrosionsprodukter kunnat studeras i detalj.
En tydlig påverkan av mikrostruktur på det initiala korrosionsförloppet har kunnat
påvisas. Korrosionsinitieringen sker företrädesvis i mer zinkrika faser för såväl Zn-
Al- som Cu-Zn-legeringar och orsakas av mikro-galvaniska effekter mellan de mer
zinkrika, mindre ädla, faserna och omgivande faser. Deponerade NaCl-partiklar
påskyndar den lokala korrosionen oberoende av mikrostruktur. Snarlika sekvenser av
korrosionsprodukter har kunnat påvisas såväl efter laboratorie- som fältexponeringar.
För Zn-Al-legeringar bildas först ZnO, ZnAl2O4 och/eller Al2O3, därefter
Zn6Al2(OH)16CO3·4H2O och Zn2Al(OH)6Cl·2H2O och/eller Zn5(OH)8Cl2·H2O. På
ren koppar bildas ett inre skikt dominerat av Cu2O, ett mellanskikt av CuCl och ett

iii
 
yttre skikt med i huvudsak Cu2(OH)3Cl. Beroende på legeringstillsats har även SnO2
och Zn5(OH)6(CO3)2 kunnat identifieras.
En mekanism för flagning av korrosionsprodukter på kopparbaserade legeringar i
kloridrika atmosfärer har utvecklats. Tendensen för flagning har visat sig vara mycket
mer uttalad på ren Cu och Cu4Sn än på Cu15Zn och Cu5Al5Zn. Skillnaden kan
förklaras med hjälp av det tidiga bildandet av Zn5(OH)6(CO3)2 och
Zn6Al2(OH)16CO3·4H2O på Cu15Zn och Cu5Al5Zn som fördröjer bildandet av CuCl,
en föregångare till Cu2(OH)3Cl. Därigenom hämmas även den observerade
volymexpansionen som sker när CuCl omvandlas till Cu2(OH)3Cl, en process som
visar sig vara den egentliga orsaken till att korrosionsprodukterna flagar. Resultaten
bekräftar barriäreffekten hos de mer svårlösliga faserna Zn5(OH)6(CO3)2 och
Zn6Al2(OH)16CO3·4H2O, vilken dels resulterar i en minskad växelverkan mellan
klorider och de legeringsytor där dessa faser kan bildas, och dels i en reducerad
metallfrigöringshastighet.

iv
Preface

This doctoral thesis provides a comprehensive understanding of atmospheric

corrosion and metal release properties of Zn-Al alloy coatings and Cu-based alloys
after both short-term laboratory, and long-term field exposures in chloride-rich
environments. The main focus is placed on multi-analytical investigations to assess
the influence of microstructure on corrosion initiation and corrosion product
evolution. Investigated materials and main topics of each scientific paper of this thesis
are schematically presented below.

v
 
List of papers 

I. The initial release of zinc and aluminum from non-treated Galvalume and the
formation of corrosion products in chloride containing media
X. Zhang, T.-N. Vu, P. Volovitch, C. Leygraf, K. Ogle, I. Odnevall Wallinder
Applied Surface Science, 258 (2012) 4351-4359

II. Atmospheric corrosion of Galfan coatings on steel in chloride-rich

environments
X. Zhang, C. Leygraf, I. Odnevall Wallinder
Corrosion Science, 73 (2013) 62-71

III. Selected area visualization by FIB-milling for corrosion-microstructure

analysis with submicron resolution
X. Zhang, C. Leygraf, I. Odnevall Wallinder
Materials Letters, 98 (2013) 230-233

IV. Corrosion and runoff rates of Cu and three Cu-alloys in marine

environments with increasing chloride deposition rate
I. Odnevall Wallinder, X. Zhang, S. Goidanich, N. Le Bozec, G. Herting, C. Leygraf
Science of the Total Environment, 472 (2014) 681-694

V. Mechanistic studies of corrosion product flaking on copper and copper-based

alloys in marine environments
X. Zhang, I. Odnevall Wallinder, C. Leygraf
Corrosion Science, 85 (2014) 15-25

Results from the following paper is partly included in the summary of this thesis:

The role of microstructure on the initial corrosion of Cu-Zn alloys in a chloride-

containing laboratory atmosphere 
X. Zhang, C. Leygraf, I. Odnevall Wallinder 
Manuscript.

In addition, some selected unpublished work is presented in the summary of this

thesis.

vi
Author contribution to the papers

The contribution of the respondent to the papers is listed below: 

Paper I. Major part of experimental work, except for AESEC and XPS/AES
measurements. Major part of data interpretation and manuscript preparation.

Paper II. Main part of experimental work, except for FEG-SEM/EDS measurements
on unexposed surfaces. Main part of data interpretation and manuscript preparation.

Paper III. Major part of experimental work, except for FIB-SEM and SKFPM
measurements. Main part of data interpretation and manuscript preparation.

Paper IV. Part of experimental work, active contribution in SEM/EDS, CRM and
GIXRD measurements. Part of data interpretation and manuscript preparation.

Paper V. Main part of experimental work, except for FEG-SEM/EDS measurements

on cross-sections. Main part of data interpretation and manuscript preparation.

vii
 
Abbreviations

AAS Atomic absorption spectroscopy

AES Auger electron spectroscopy
AESEC Atomic emission spectroelectrochemistry
AFM Atomic force microscopy
BSE Backscattered electrons
CRM Confocal Raman micro-spectroscopy
DTGS Deuterated triglycine sulfate
EDS Energy dispersive x-ray analysis
EMF Standard electromotive force
ESEM Environmental scanning electron microscopy
FEG Field emission gun
FIB-SEM Focused ion beam-scanning electron microscopy
FTIR Fourier transform infrared
GDOES Glow discharge optical emission spectroscopy
GF Graphite furnace
GIXRD Grazing incidence x-ray diffraction
IR Infrared
IRAS Infrared reflection absorption spectroscopy
MCT Mercury cadmium telluride
NHE Normal hydrogen electrode
New revised VDA corrosion test method
N-VDA
Standard SEP 1850 VDA 621-415 B
OCP Open circuit potential
OM Optical microscopy
SCE Saturated calomel electrode
SE Secondary electrons
SEM Scanning electron microscopy
SHE Standard hydrogen electrode
SKFPM Scanning Kelvin probe force microscopy
XPS X-ray photoelectron spectroscopy
XRD X-ray diffraction
 

viii
Table of Contents

Abstract................................................................................................................................... i
Sammanfattning .................................................................................................................. iii
Preface.................................................................................................................................... v
List of papers ........................................................................................................................ vi
Author contribution to the papers.....................................................................................vii
Abbreviations .................................................................................................................... viii
1 Introduction ..................................................................................................................... 1
1.1 Motivation and scope .................................................................................................... 1
1.2 Atmospheric corrosion .................................................................................................. 3
1.2.1 Metal surface interaction with the atmosphere ...................................................... 3
1.2.2 Atmospheric gases and particles ............................................................................ 4
1.3 Zn-Al and Cu-based alloys............................................................................................ 5
1.3.1 Zn-Al alloy coatings ............................................................................................... 5
1.3.2 Cu-based alloys ...................................................................................................... 6
1.4 Atmospheric corrosion of Zn-Al and Cu-based alloys.................................................. 7
1.4.1 Corrosion product formation and metal release .................................................... 7
1.4.2 Microstructure-related galvanic corrosion ............................................................ 9
2 Materials and methods ................................................................................................. 12
2.1 Materials and surface preparation ............................................................................... 12
2.1.1 Materials............................................................................................................... 13
2.1.2 Surface preparation .............................................................................................. 13
2.2 Exposure conditions .................................................................................................... 14
2.2.1 Laboratory wet/dry cycle exposure (Papers II, V) ............................................... 14
2.2.2 Laboratory immersion and flow-cell tests (Paper I) ............................................ 15
2.2.3 Long-term field exposure (Papers I, II, IV, V)...................................................... 15
2.2.4 Accelerated N-VDA test (non-published data) ..................................................... 16
3 Analytical techniques .................................................................................................... 17
3.1 Scanning electron microscopy with x-ray microanalysis (SEM/EDS) ....................... 18
3.1.1 Environmental - SEM (ESEM) ............................................................................. 19
3.1.2 Focused ion beam - SEM (FIB-SEM) ................................................................... 20

ix
 
 3.2 Infrared reflection absorption spectroscopy (IRAS) ................................................... 20
3.3 Confocal Raman micro-spectroscopy (CRM) ............................................................. 22
3.4 Grazing incidence x-ray diffraction (GIXRD) ............................................................ 23
3.5 Scanning Kelvin probe force microscopy (SKPFM) .................................................. 24
3.6 X-ray photoelectron spectroscopy/ Auger electron spectroscopy (XPS/AES) ........... 25
3.7 Glow discharge optical emission spectroscopy (GDOES) .......................................... 25
3.8 Optical microscopy (OM)/ Stereomicroscopy ............................................................ 26
3.9 Atomic absorption spectroscopy (AAS) ..................................................................... 26
3.10 Atomic emission spectroelectrochemistry (AESEC) ................................................ 27
4 Influence of microstructure on corrosion initiation ................................................... 28
4.1 The eutectic structure of Galfan consists of an η-Zn matrix and β-Al lamellas and
rods of lower surface nobility compared with the matrix, and are separated by β-Al grain
boundaries in which ZnO and Al2O3 preferentially form. (Paper III) ............................... 28
4.2 Corrosion initiation observed for Galfan in the zinc-richer η-Zn phase adjacent to the
less zinc-rich β-Al phase. Both carbonate and chloride-containing phases are formed in
humidified air and in the presence of NaCl. (Paper II) ..................................................... 30
4.3 Selective zinc release and corrosion initiation in the zinc-rich phase observed for
Galvalume in chloride containing media. Long-term correlation observed between the
released zinc fraction and the surface coverage of zinc and aluminum-rich corrosion
products. (Paper I) ............................................................................................................. 34
4.4 The dual-phase structure of Cu40Zn consists of zinc-richer β-phase crystals of lower
surface nobility than the α-phase. Corrosion initiation is observed in the β-phase at low
pre-deposition of NaCl. (non-published data) ................................................................... 37
4.5 Microgalvanic effects on a Cu-Zn patterned sample with pre-deposited chlorides
result in a radial distribution of corrosion products from the Cu cathode to the Zn anode
upon cyclic exposures in humidified air. (non-published data) ........................................ 39
5 Corrosion product evolution and characteristics......................................................... 43
5.1 Severe corrosion product flaking observed for Cu and Cu4Sn in chloride-rich
environments is primarily connected to the presence of nantokite. Minor effects observed
for Cu15Zn and Cu5Al5Zn. (Paper V).............................................................................. 43
5.2 Transformation of nantokite to paratacamite results in volume expansion within the
patina causing corrosion product flaking for Cu and Cu4Sn. (Paper V)........................... 46
5.3 The initial formation of Zn- and Zn/Al-hydroxycarbonates reduces the sensitivity of
Cu15Zn and Cu5Al5Zn to chloride-induced corrosion, and also the release of zinc from
Galfan at marine conditions. (Papers II, IV, V) ................................................................ 51

x
 5.4 Similar corrosion products form on Galfan and bare Zn sheet and on Galvalume and
bare Al sheet, respectively, upon accelerated chloride test conditions. (non-published
data) ................................................................................................................................... 53
5.5 Laboratory set-ups with exposures to chloride-rich environments were able to
successfully reproduce the predominating corrosion products formed at marine outdoor
conditions for the Zn-Al coatings, bare Cu sheet and the Cu-based alloys. (Papers I, II,
IV, V) ................................................................................................................................ 56
5.5.1 Zn-Al alloy coatings ............................................................................................. 56
5.5.2 Cu and Cu-based alloys........................................................................................ 57
5.6 General scenarios for patina evolution established for Zn-Al coatings and corrosion
product flaking mechanisms proposed for Cu-based alloys in chloride-rich atmospheric
environments. (Papers II, V) ............................................................................................. 57
5.6.1 Zn-Al alloy coatings ............................................................................................. 57
5.6.2 Cu and Cu-based alloys........................................................................................ 59
6 Summary and outlook .................................................................................................. 61
Acknowledgements ............................................................................................................. 65
References ............................................................................................................................ 67

xi
 
 

xii
1 Introduction

1.1 Motivation and scope

Atmospheric corrosion of materials at outdoor conditions is a corrosion process
that results in large economic losses in the society. Increased levels of corrosive
pollutants have in different parts of the world resulted in dramatic deterioration of
metal surfaces used in outdoor constructions, in vehicles and other surfaces of the
cultural heritage [1], whereas corrosion effects have been less severe in areas of
reduced pollutant levels [2]. Prevention measures against atmospheric corrosion in
high-technology societies have been reported to account for almost half the total
estimated cost for corrosion protection [3].
Since the nature of atmospheric corrosion is inherently complicated, in-depth
fundamental understanding of prevailing corrosion processes is of great importance
for the society, e.g. for regulators and the industry [1]. The use of metals and alloys at
outdoor conditions is of high necessity in the modern society due to their excellent
mechanical properties and good corrosion resistance. Atmospheric corrosion of alloys
is even more complex compared with the pure metals, as the mechanisms depend not
only on prevailing environmental conditions but also on alloying elements and
differences in microstructure and surface characteristics. The presence of e.g.
secondary phases, grain boundaries, and inclusions may negatively affect the overall
corrosion performance [4].
This doctoral thesis comprises extensive studies that contribute to a more
comprehensive understanding of atmospheric corrosion and metal release processes
of commercial Zn-Al alloys (of relevance for automotive applications) and Cu-based
alloys (used in outdoor construction applications) in chloride-rich environments. The
thesis includes both short-term laboratory and long-term marine field exposures
aiming to assess initial atmospheric corrosion mechanisms and the evolution of
corrosion products in chloride-rich environments, and their link to microstructural
features of the investigated alloys. The research approach is summarized in Fig.1.1.
The influence of humidity and chlorides has been elucidated through successive
short-term controlled laboratory exposures and the use of different near surface- and
bulk sensitive analytical tools. Long-term data from marine field exposures has been
used to ensure realistic laboratory simulations. Microstructure-related corrosion
initiation and corrosion product evolution were investigated in-situ using IRAS
(infrared reflection absorption spectroscopy) and ESEM/EDS (environmental

1
 
scanning electron microscopy with x-ray microanalysis), and ex-situ with SEM/EDS,
CRM (confocal Raman micro-spectroscopy), GIXRD (grazing incidence x-ray
diffraction), SKPFM (scanning Kelvin probe force microscopy), XPS/AES (x-ray
photoelectron spectroscopy/ Auger electron spectroscopy), and GDOES (glow
discharge optical emission spectroscopy). Metal release processes were evaluated in-
situ with AESEC (atomic emission spectroelectrochemistry) and ex-situ with AAS
(atomic absorption spectroscopy).
Research activities within this doctoral study are connected to an EU project
(Autocorr, RFSR-CT-2009-00015) focusing on corrosion of heterogeneous metal-
metal assemblies in the automotive industry, and to a long-term international industry
consortium project focusing on atmospheric corrosion and environmental metal
dispersion from outdoor construction materials. The test materials were supplied via
Arcelor Mittal, France, KME, Germany and Aurubis, Finland. The experimental work
was performed at the Division of Surface and Corrosion Science at KTH in
collaboration with colleagues at Ecole Nationale Supérieure de Chimie de Paris,
France and Politecnico di Milano, Italy.

Figure 1.1. Summary of main aspects investigated in this doctoral thesis.

2
1.2 Atmospheric corrosion
The science of atmospheric corrosion was evolved by the pioneering work of
Vernon [5] almost a century ago. Atmospheric corrosion is the result of an interaction
between a material, mostly a metal, and its surrounding atmosphere. The process is
triggered by relative humidity levels that result in a thin aqueous layer at the surface
of the material [1]. The water layer may vary from monomolecular thickness to clearly
visible water films depending on prevailing humidity conditions [3]. Environmental
pollutants will interact with the aqueous film and influence the corrosion process in
different ways. As an interdisciplinary field of science, atmospheric corrosion has
become more widely investigated during the past decades assessing an improved
molecular understanding of corrosion processes [6], and environmental effects induced
by released metals from corroded surfaces [7, 8].
1.2.1 Metal surface interaction with the atmosphere
The field of atmospheric corrosion integrates diverse subjects such as chemistry,
electrochemistry, material science and physics. Atmospheric corrosion is complex
since prevailing processes take place in several regimes, at the interfaces between the
gaseous phase and the liquid phase, and between the liquid and the solid phase [1].
Figure 1.2 schematically demonstrates the multi-regime (gas, liquid and solid phases
separated by two interfaces) involved in atmospheric corrosion for a given metal
surface.

Figure 1.2. Different regimes involved in atmospheric corrosion.

3
 
 In the initial stage of atmospheric corrosion, water vapor instantly reacts with the
metal surface that becomes hydroxylated. Further exposure in humid air results in the
adsorption of water as monomolecular layers, or as a thin aqueous adlayer [1].
Atmospheric constituents, gaseous pollutants and airborne salt particles deposit at
the intermediate stage on the metal surface and dissolve to different extent within the
thin adlayer, processes that result in a variety of chemical and electrochemical
interfacial reactions [1]. Unevenly distributed water droplets result in local
electrochemical corrosion cells that form spatially separated anodes and cathodes [9].
The dominating electrochemical reactions for most corrosion processes include metal
oxidation and oxygen reduction:
M → M n+ + ne- Anodic reaction
O2 + 2H2O + 4e- → 4OH- Cathodic reaction
Dissolved metal ions can coordinate with counterions present in the aqueous layer,
and eventually precipitate into a solid phase (nucleation of corrosion products), when
the concentration of ion pairs in the aqueous layer reaches supersaturation.
In the final stage of atmospheric corrosion, the number and size of precipitated
nuclei increase with prolonged exposure until eventually they completely cover the
metal surface, often referred to as a corrosion product layer.
1.2.2 Atmospheric gases and particles
The most important atmospheric constituents of importance for atmospheric
corrosion include H2O and CO2, dominantly present in the atmosphere as corrosion
stimulators. Other corrosive constituents include atmospheric gases such as sulfur
dioxide (SO2), nitrogen dioxide (NO2), ammonia (NH3) and ozone (O3), organic acids,
and airborne particles containing e.g. chlorides (Cl-), sulfates (SO42-) and nitrates
(NO3-) [10, 11].
Humidity is a measure of the quantity of water vapor present in the atmosphere.
The relative humidity (RH) is defined as the ratio between the absolute humidity and
the saturation quantity [11]. Due to climatic variations, RH significantly fluctuates
during the day, and from day to day in open atmosphere, important factors together
with temperature variations for the resulting aqueous layer on a metal surface. This
layer is essential to initiate atmospheric corrosion as it acts as a medium for
electrochemical and chemical reactions as well as a solvent for atmospheric
constituents, as discussed above [1].
CO2 is a natural constituent of the atmosphere and also emitted by anthropogenic
activities such as fossil fuel combustion. The average atmospheric concentration of

4
CO2 is about 350-400 ppm. Even though it is relatively unreactive in ambient air, it is
soluble in water and forms bicarbonate (HCO3-) and carbonate ions (CO32-) that for
many metals have a major influence on the corrosion process [1]. The most significant
effect of CO2 on atmospheric corrosion is its participation in the formation of
corrosion products on non-ferrous metals [9]. Prevailing corrosion processes have been
extensively investigated and been validated in the scientific literature, in particular for
chloride-rich environments [12-16].
Chloride-rich aerosols are the dominating pollutants in marine environments that
for many metals/alloys accelerate the corrosion rate by several orders of magnitude
[17]
. These aerosols are suspensions of small liquid or solid particles originating from
salt spray and fog in the vicinity of the seashore [11]. Deposition of such aerosols
provides a relatively corrosive aqueous surface layer of high conductivity in which
the chloride ion interacts with the surface initiating corrosion, e.g. pitting. Depending
on metal/alloy surface oxide properties, chlorides can locally destroy native surface
oxides and hydroxides of different passive properties. The importance of chlorides on
the atmospheric corrosion of metals has been extensively investigated in the scientific
literature [18-22].
Gaseous SO2 is a common environmental pollutant in the atmosphere that is
corrosive for many metals [1], and originates predominantly from combustion of coal,
oil, and gasoline. SO2 is predominantly present in urban and industrial atmospheres
and is easily dissolved in water forming different sulfur species including e.g. HSO3-
and SO42- both in airborne water droplets and in the aqueous surface layer at the metal
surface [11]. This layer often obtains a reduced local pH (often below 4.5) that can, for
some metals, reduce the oxide stability and increase the corrosion rate [1, 9]. Its effects
have been extensively studied for different metals, also in combination with other
pollutants such as CO2, NO2, chlorides and O3, due to its significance at atmospheric
conditions [18, 20, 23, 24].

1.3 Zn-Al and Cu-based alloys

1.3.1 Zn-Al alloy coatings
Hot-dip galvanized zinc coatings containing aluminum on steel substrates have
been frequently used in many applications of atmospheric relevance due to their
sacrificial protection of steels and beneficial corrosion resistance [25, 26]. Two different
commercial Zn-Al alloy coatings on steel, GalfanTM (Zn-5wt% Al) and GalvalumeTM
(Zn-55wt% Al), of widespread use in automotive, construction and industrial
applications [27], have been investigated in this thesis.

5
 
 The Galfan coating contains 5 wt% Al, which is very close to the eutectic point in
the Zn-Al system [28, 29], and up to 0.05 wt% mischmetal (lanthanum and cerium). Due
to its high corrosion resistance, superior ductility and forming properties it is often
used in automotive applications [30]. The microstructure is characterized by a two-
phase structure with a zinc-rich proeutectoid phase (Al/(Al+Zn) <5wt%) and a
eutectic phase (Al/(Al+Zn): 5-10 wt%) consisting of beta (β) aluminum (5-25 wt%
Al) and eta (η) zinc-rich lamellas (<5 wt% Al) [31-34].
The Galvalume coating has a significantly higher content of aluminum compared
with Galfan and low amount of silicon (55wt% Al-43.4 wt % Zn-1.6 wt % Si [35]). The
corrosion resistance of Galvalume coatings on steel is remarkably improved compared
with a bare galvanized steel surface of equivalent coating thickness upon exposure in
marine and industrial atmospheres. The coating efficiently protects the substrate at
scratches and cut edges.[36]. The Galvalume coating has a two-phase microstructure
with an aluminum-rich dendritic phase (Al/(Al+Zn): 60-80 wt%) and a zinc-rich
interdendritic phase (Al/(Al+Zn): 20-40 wt%) [14, 37].
Differences in cooling rate, annealing time and nucleation temperature upon
solidification influence the microstructure, and subsequently the corrosion resistance
of both Galfan and Galvalume [38-40].
1.3.2 Cu-based alloys
Copper in its pure or alloyed state forms a large group of industrially very important
materials. Depending on alloying elements, the desirable properties range from high
electrical conductivity, corrosion resistance, wear resistance, tensile strength,
soldering and joining characteristics, to an appealing visual appearance. Below
follows a few examples of copper-based alloys used in atmospheric applications of
relevance for outdoor constructions such as roofs, claddings and facades.
Bronze alloys often contain tin as the main element. This alloy was developed
already four thousand years ago. The tensile strength and corrosion resistance of the
alloys are for most applications superior compared to bare copper sheet. Bronze alloys
contains, similar to bare copper, often small amounts of phosphorus that further
increase the alloy hardness and wear resistance [41].
Brass alloys consist primarily of copper and zinc in different proportions and have
good strength and ductility [41]. Alpha () brass with up to 35 wt% zinc consists
primarily of one phase with face-centred cubic crystal structure. The - brasses
(sometimes called duplex brasses) contain 35-45 wt% zinc and consist of -dendrites
in a body-centred cubic -matrix [42]. The dual-phase structure consists, according to
literature findings, of precipitated -phase crystals in a β-phase matrix [43, 44]. The -

6
phase, of higher zinc content than the -phase, exhibits a characteristic plate-type
morphology with plates orientated in different directions [42].
Cu-based alloys with aluminum (5 wt%) and zinc (5 wt%) have during recent years
found an increasing use. Their welding and soldering properties are very good and
they are malleable, regardless of temperature and rolling direction [45].

1.4 Atmospheric corrosion of Zn-Al and Cu-based alloys

1.4.1 Corrosion product formation and metal release
Atmospheric corrosion of zinc at natural weathering conditions has been widely
investigated [19, 46-52]. A general evolution scheme of corrosion product formation on
zinc was established by Odnevall and Leygraf [53]. A thin layer of amorphous
hydroxycarbonate (Hydrozincite, Zn5(OH)6CO3) forms rapidly in any humid-
containing atmosphere. In humid, low polluted environments, this phase often
gradually evolves into its crystalline form. If chlorides are also present in the
atmosphere, zinc hydroxychloride (Simonkolleite, Zn5(OH)8Cl2·H2O) is locally
formed and eventually evolves into a sodium zinc hydroxychlorosulfate (Gordaite,
NaZn4Cl(OH)6SO4·6H2O). The presence of SO2 and sulfates results in the formation
of different zinc hydroxysulfates (Zn4SO4(OH)6·nH2O) and, in the presence of
chlorides, also zinc chlorohydroxysulfate (Zn4Cl2(OH)4SO4·5H2O) may form.
Atmospheric corrosion processes of zinc at laboratory-simulated conditions have been
investigated in a large number of studies [54-59]. In-situ surface analyses reveal
Zn5(OH)8Cl2·H2O as the main corrosion product formed on bare zinc sheet at
chloride-rich conditions [18].
Extensive investigations are also reported in the scientific literature on corrosion
rates and long-term corrosion product formation on zinc-aluminum coatings on steel
at atmospheric conditions [19, 36, 60-64]. Zn6Al2(OH)16CO3·4H2O as well as
Zn2Al(OH)6Cl·2H2O [65] have, in addition to zinc hydroxychlorides and carbonates,
been identified in several investigations [66-68] for Zn-Al coatings. Al(OH)3 has been
identified on Galvalume at different exposure conditions [60, 69] and Al2(OH)6·4H2O
and AlZn sulfate hydrates after long term field exposures [60].
Significant knowledge exists in the scientific literature on patina formation on
copper at marine exposure conditions, and to some extent also for some copper-based
alloys in chloride-rich environments [50, 70-77]. Cuprite (Cu2O), and to some extent CuO,
are the initial phases in the evolution of the copper patina at sheltered marine exposure
conditions. Interaction with chlorides results in the formation of nantokite (CuCl)
which typically transforms to atacamite or the isomorphous phase paratacamite
(Cu2(OH)3Cl) as end corrosion products [70]. These constituents have also been

7
 
identified within the patina on bare copper at unsheltered marine exposure conditions
[71]
, and also been observed at laboratory conditions in humidified air with pre-
deposited NaCl [12, 72].
As evidenced from a recent review [78] has the atmospheric corrosion of Cu-alloys
such as bronze or brass in chloride-dominating environments been significantly less
extensively studied compared with bare copper. Similar patina constituents as formed
on bare copper have also been observed within the patina on restored ancient bronzes
[79-81]
. Nantokite (CuCl), trapped within the patina of archeological bronzes, and
paratacamite (Cu2(OH)3Cl) are important constituents that govern the so-called
bronze disease, which is a progressive corrosion process mainly based on the
conversion of nantokite to paratacamite. This process leads to volume expansion and
subsequent cracking or flaking of formed corrosion products [80, 81]. Tin oxide (SnO2)
has been identified within the patina in different environments [82, 83]. Amorphous
and/or crystalline zinc hydroxycarbonate, hydrozincite (Zn5(OH)6(CO3)2) and zinc
oxide (ZnO) that cover large surface areas have been observed on brass at sites of low
chloride deposition rates [75]. Zinc oxide has been identified as the main corrosion
product formed at laboratory conditions in humidified air with reduced CO2-
concentrations [84].
The interaction of metal surfaces and surrounding environments results not only in
corrosion and formation of corrosion products and their evolution but also in the
release of dissolved metals from the patina. This portion can be transported from the
surface by means of atmospheric precipitation. Metal release (patina dissolution)
occurs at the interface between the corrosive media and the patina, and should be
distinguished from corrosion (oxidation) [85] taking place at the bare metal surface.
The concern of dispersed metals into the environment and potential adverse effects
has gradually increased world-wide during the past decades [86], primarily as a
consequence of considerably reduced emissions of metals from point sources.
Several investigations have during recent decades explored the effect of metal
release of zinc and copper from outdoor construction materials [8, 61, 76, 86-92]. Results
from long-term field exposures and parallel laboratory studies have confirmed that the
metal release process is largely dependent on e.g. the corrosion product composition
and characteristics and to prevailing environmental conditions. It has been reported
that the zinc release pattern from Galvalume during long-term field exposures follows
the same time-dependence as the surface coverage of zinc-rich and aluminum-rich
corrosion products [14]. The release of copper from copper alloys exhibits typically
lower rates compared with bare copper sheet [75]. Similar observations have been
reported for the release of zinc from Galvalume compared with bare zinc sheet [14]. It
should be taken into account that corrosion products within the patina on alloys

8
become enriched in specific alloying elements that to different extent improve the
solubility and barrier properties of the patina and thereby in reduced release rates.
1.4.2 Microstructure-related galvanic corrosion
Galvanic corrosion is an electrochemical process occurring when two dissimilar
metals or alloys are in electrical contact in the presence of an electrolyte. The driving
force for the process is the difference in electrode potential between the materials [11].
The general principle of galvanic corrosion is displayed in Fig.1.3 [93].

Figure 1.3. Schematic illustration of the principle of galvanic corrosion.

When two metals are coupled in a conductive electrolyte, the polarity and direction
of electron flow can be determined from their difference in potential, indicating their
galvanic behavior [11]. Table 1.1 provides examples of standard electrode potentials
for different metals and predictions of relative nobilities in the galvanic series [94]. The
metal of lower potential usually acts as anode and will initially preferentially undergo
corrosion in the galvanic couple. However, since the electromotive series (EMF) only
considers pure metals in pure water without considering the presence of surface oxides
or the behavior of alloys, the actual behavior of the galvanic couple at atmospheric
conditions may be very different from what is proposed by the EMF-series. As an
example, Al is considered more active than Zn (-1.66 V vs. -0.76 V, see Table 1.1) in
the standard EMF series. However, the presence of the native Al2O3 surface oxide on
Al makes it more passive compared with Zn in a Zn-Al couple, from which follows
that Zn becomes more active and protects the aluminum surface, in particularly in
seawater (-0.79 V vs. -1.03 V, , see Table 1.1) [27, 95].
Galvanic corrosion cells can be established both on a macroscopic and a
microscopic level. On a microstructural level microgalvanic couples can be formed
between different phases or other microstructural features within an alloy, in terms of

9
 
coupling of two metals. The active phase or feature in the microgalvanic cell acts as
a micro-anode and is preferentially corroded, which is the effect of microgalvanic
corrosion [96]. The differences in nobility of an alloy between different microstructural
features and phases, and sites prone to corrosion initiation can be observed by
measuring differences in relative surface Volta potential [97-99] using the scanning
Kelvin probe technique. The method measures differences in electrostatic potential
over a surface, if any. The advancement of local probing techniques has enabled the
exploration of corrosion phenomena and the interplay between local galvanic
corrosion processes and microstructural features with high lateral resolution [14, 84, 100].

Table 1.1. Standard electromotive force (EMF) series of different metals relative to
the standard hydrogen reference electrode (SHE) (Standard electrode potentials in
H2O at 25 and 1 bar), and the corresponding galvanic series in seawater, relative
to the saturated calomel reference electrode (SCE) [27, 95].
Potential /VSCE Galvanic series
Electrode Half-cell reaction Potential /VSHE
in seawater in seawater
Cu+ + e- → Cu 0.52 Noble
Cu -0.36
Cu2+ + 2e- → Cu 0.34
Fe3+ + 3e- → Fe -0.04
Fe -0.61
Fe2+ + 2e- → Fe -0.45
Al Al3+ + 3e- → Al -1.66 -0.79
Zn Zn2+ +2e- → Zn -0.76 -1.03 Active

Scarce literature findings exist regarding corrosion during early stages of

atmospheric corrosion of Galfan and the relation to its microstructure. This may be
connected to its complex and fine (sub-micron sized) and heterogeneous
microstructure. An improved corrosion resistance of the proeutectoidic η-Zn phase
compared with the eutectic colonies has been reported by Tang et al. [101]. According
to Yang et al. [102] is the eutectic phase of superplastic Zn-Al alloys (4, 8, 12, 16 wt%
Al) prone to preferential corrosion upon immersion in simulated acid rain.
The spangled microstructure of Galvalume has been extensively investigated and
reported in the scientific literature. It consists of aluminum-rich dendritic areas and
interdendritic zinc-rich regions containing silicon [35, 37]. Corrosion initiation has been
reported to take place in zinc-rich interdentritic areas [35, 36, 60, 68], whereas corrosion of
aluminum-rich dendritic phases preferentially takes place after longer exposure
periods, or at corrosive conditions [35]. Corrosion of Galvalume results in selective
release of alloy constituents [103] that typically involve selective release of the less
noble element, leaving a surface enriched in the more noble element. Prevailing local
surroundings will possibly be able to predict whether aluminum or zinc is the most

10
active element. However, as corrosion products gradually evolve on the surface,
selective release results in the enrichment of one or more alloying element in the alloy
phase beneath the surface oxide [104-108].
Several studies in the scientific literature have shown the initial corrosion of -
brass and the formation of micrometer-sized zinc-rich granules and the preferential
release of zinc at atmospheric conditions [75, 84, 109]. Forslund et al. have reported
initiation of local dissolution in zinc-rich areas of lower surface potential compared
with the matrix on Cu20Zn in diluted NaCl solution [110]. Microgalvanic effect may
also result in selective leaching of zinc from brass, dezincification, followed by
weakened porous copper-rich areas [109, 111]. However, limited scientific understanding
exists on the microgalvanic corrosion between the -phase and the more zinc-rich -
phase of duplex brass at initial stages of atmospheric corrosion.

11
 
2 Materials and methods

2.1 Materials and surface preparation

Different bare metals and alloys were investigated to assess initial atmospheric
corrosion mechanisms and metal release processes upon exposure to different
chloride-rich environments. Table.2.1. summarizes the materials, their corresponding
bulk nominal composition and exposure conditions that have been investigated within
this doctoral thesis (with reference to the corresponding Paper).

Table. 2.1. Summary of materials used within the scope of the different Papers of this thesis.
(* non-published data presented in the thesis summary only.)
Name Composition (wt %) Exposure conditions Used in Papers
Wet/dry cycle
95Zn-5Al II, III 
Galfan™ Marine field
(0.05 Ce and La)
N-VDA tests
Immersion and
flow-cell tests
Galvalume™ 55Al-43.4Zn-1.6Si I
Marine field
N-VDA tests
Zn sheet 99.99 Zn N-VDA tests *
Al sheet 99.99 Al N-VDA tests *
Wet/dry cycle
Cu sheet 99.98 Cu IV, V
Marine field
Cu4Sn Wet/dry cycle
96Cu-4Sn IV, V
(Bronze) Marine field
Cu15Zn Wet/dry cycle
85Cu-15Zn IV, V
(Brass) Marine field
Wet/dry cycle
Cu5Al5Zn 89Cu-5Al-5Zn-1others IV, V
Marine field
Cu40Zn
60Cu-40Zn Wet/dry cycle *
(Brass)
Zn substrate with
CuZnP patterned deposited Cu Wet/dry cycle *
islands

12
2.1.1 Materials
Commercial Zn-Al coated steel samples (Galfan and Galvalume) and bare zinc and
aluminum sheets were supplied via Arcelor Mittal, France. The Zn-Al coatings were
applied on steel via a hot-dip process that generated a coating thickness of 7 and 25
µm for Galfan and Galvalume, respectively [30].
Commercial Cu and Cu alloys samples (bare Cu sheet, Cu4Sn, Cu15Zn, Cu40Zn
and Cu5Al5Zn) were provided via KME, Germany and Aurubis, Finland. More
detailed information on their nominal bulk alloy composition (except for Cu40Zn) is
provided in Table 1 in Paper IV [112].
The patterned copper-zinc samples (CuZnP) were kindly provided by Xiamen
University, China. Sputtered copper islands sized of 2020 µm (100 nm in height),
with a spacing of 20 µm, were deposited onto a bare zinc substrate. The overall
elemental surface coverage was theoretically calculated to 74.3% for zinc, and 25.4%
for copper [113]. Details regarding the patterned copper-zinc samples are given
elsewhere [113].
2.1.2 Surface preparation
Galfan samples for laboratory wet/dry cycle exposures were cut to a dimension of
11 cm for in-situ IRAS and ESEM exposures. The utmost high temperature oxide
layer formed during the hot-dip process was removed for most samples by gentle
polishing using a 0.25 μm diamond paste. All samples were cleaned ultrasonically in
analytical grade ethanol for 10 min, dried by cold nitrogen gas and stored in a
desiccator overnight.
Galvalume samples for laboratory immersion tests were cut to a dimension of 40.5
cm. The reverse side and all edges of the samples were sealed with a transparent non-
metal containing polish three times. All flow-cell tests were performed using an
exposed surface area of 10.5 cm.
Bare Zn and Al sheet, Galfan and Galvalume samples for the N-VDA tests were
cut to a dimension of 25 cm. The Zn and Al samples were mechanically wet ground
down to 1200 grit, and the Galfan and Galvalume samples were gently polished using
a 0.25 μm diamond paste.
Bare Cu sheet and the Cu-based alloy samples were cut to a dimension of 11 cm
for in-situ IRAS exposures and 25 cm for climatic chamber exposures. Each sample
was mechanically wet ground down to 2400 grit and polished with diamond paste
down to 1 or 0.25 μm. All freshly polished samples were, prior to analyses,

13
 
ultrasonically cleaned in analytical grade ethanol for 10 min and dried by cold
nitrogen gas before stored in a desiccator overnight.
No polishing was possible for the patterned copper-zinc samples. After ultrasonic
cleaning in ethanol, the samples were immersed in 5 wt% amidosulfonic acid (ASA,
H3NSO3) for approximately one second to chemically remove the outermost surface
oxide. The samples were dried by cold nitrogen gas and stored in a desiccator
overnight.
A synthetic nantokite layer (CuCl) was grown on the bare Cu surface according to
a procedure described elsewhere [114, 115]. After the same surface preparation as above,
bare Cu samples were immersed for 1 h in a saturated CuCl2·2H2O solution (>78g of
CuCl2·2H2O per 100mL of deionized water). The samples were then rinsed with
deionized water followed by immediate drying using cold nitrogen gas and stored in
a desiccator overnight.

2.2 Exposure conditions

2.2.1 Laboratory wet/dry cycle exposure (Papers II, V)
Parallel in-situ experiments on Galfan samples were carried out by means of ESEM
(environmental - scanning electron microscopy) and in-situ IRAS (infrared reflection
absorption spectroscopy) upon exposure to cyclic exposure conditions, schematically
displayed in Fig.2.1 (NaCl pre-deposition (0 or 4/0.1 μg NaCl/cm2), the first cycle 4
h (RH 90%) and 2 h (RH 0%), the second cycle 16 h (RH 90%) and 2 h (RH 0%)).
These cycles were repeated several times. Parallel exposures were conducted at 70%
RH. SEM imaging of surface features and IRAS spectra of corrosion product
formation were generated during the dry cycles.
Parallel experiments on bare Cu sheet and Cu alloys were conducted by means of
in-situ IRAS and climatic chamber exposures. Wet/dry cycle experiments were
carried out following the same cyclic exposure conditions as shown in Fig.2.1. All
climatic chamber exposures were conducted in a WEISS WK1000 climatic chamber.
Different samples (Cu sheet, Cu4Sn, Cu15Zn, Cu40Zn and Cu5Al5Zn) were attached
on Plexiglas fixtures and exposed at 45˚ from the horizontal. All samples were
exposed in parallel, withdrawn after 1, 2, 6 and 14 cycles (corresponding to 6 h, 1, 3,
7 days, respectively) and analysed ex-situ.
NaCl (in a saturated 99.5% ethanol solution) was applied prior to exposure using a
transfer pipette providing a relatively homogeneous distribution of NaCl crystals upon
ethanol evaporation. The amount of deposited NaCl was weighed (Mettler Toledo
Excellence microbalance) and normalized to the geometric surface area.

14
Figure 2.1. Schematic illustration of wet/dry cycles during the laboratory exposures (Paper
II).

2.2.2 Laboratory immersion and flow-cell tests (Paper I)

Immersion experiments and flow-cell tests were performed on Galvalume samples
in synthetic rain water (pH 4.4.) [116] of modified chloride content (0.01 and 0.3 mM)
and in synthetic seawater (pH 8.1) [117]. Chemical composition of each media is given
in Tables I and II in Paper I. These acid- and chloride containing media were selected
to enable comparison with atmospheric field data, and of particular relevance for
automotive applications.
For the immersion tests, the samples were attached at the bottom of polypropylene
vessels (2965 cm). Triplicate samples and one blank (no sample) were exposed in
parallel. The vessels were gently agitated using a bi-linear shaking table, moving the
media over the sample surface. Similar exposure time periods and specific solution
volumes were selected for the immersion tests as investigated in the flow-cell test.
For the flow-cell tests, AESEC (atomic emission spectroelectrochemistry) was
employed for real-time measurements of released metals as a function of time
downstream from an electrochemical flow cell at open circuit potential (OCP) and at
an applied anodic potential (-400 mV vs. NHE). A sample area of 0.5 cm2 was exposed
to the continuously renewed flowing test media for 3000 s (50 min). These
investigations were performed at Ecole Nationale Supérieure de Chimie de Paris,
France.
2.2.3 Long-term field exposure (Papers I, II, IV, V)
Non-treated Galfan and Galvalume samples were exposed at unsheltered
conditions at the marine site of Brest (Sainte Anne du Portzic), France for 5 years
(SO2 < 3 µg/m3, precipitation: 800-1000 mm/y, chlorides deposition rates: 7-8757

15
 
mg/m2 d). The evolution of corrosion products was studied after 2, 4, 12, 26 and 52
weeks and 5 years. All surfaces were exposed 5-10 m from the waterline, and exposed
at an inclination of 45º from the horizontal, facing south, according to the ISO 17752
standard for metal runoff rate measurements [118].
Copper sheet, Cu4Sn, Cu15Zn and Cu5Al5Zn were exposed at the same site and
exposure conditions (45° from the horizontal, facing south) for 3, 6 months, and 1, 2
and 3 years (starting from Nov, 2009). The surfaces were exposed at four sites of
increasing distance from the coastal line (site 1 - Military harbour: < 5m; site 2 - St.
Anne: 20-30 m; site 3 - St Pierre: 1.5 km; site 4 - Langonnet: 40 km). Corrosion
product formation studies of this thesis include measurements at the site closest to the
coastal line, i.e. site 1 with measured deposition rates of chlorides varying between
300-1500 mg/ m2 d (large seasonal differences).
2.2.4 Accelerated N-VDA test (non-published data)
Bare Zn and Al sheet, Galfan and Galvalume samples were exposed in a WEISS
WK1000 climatic chamber, following the cycles of accelerated N-VDA tests (New
revised VDA Corrosion Test Method, Standard SEP 1850 VDA 621-415 B). The N-
VDA test is a new accelerated corrosion test developed by the German Association of
automotive industry (VDA) and the German Steel Association (VDEh) [119]. The test
is schematically illustrated in Fig. 2.2. Duplicate samples of each material, attached
on Plexiglas fixtures and exposed at 45˚ from the horizontal, were withdrawn after
each cycle (day) of the N-VDA test during one week and analysed ex-situ. The N-
VDA accelerated test was conducted at VoestAlpine, Austria.

Figure 2.2. Schematic illustration of the accelerated N-VDA test cycles. (cited from appendix
1.1 in ref. [120])

16
3 Analytical techniques

Highly surface sensitive and non-destructive analytical techniques were employed

for in-depth analysis and time-dependent measurements of changes in microstructure,
corrosion product initiation and evolution, surface composition and release of metals.
Table.3.1. summarizes the different techniques and main information provided.

Table 3.1. Compilation of analytical techniques (and abreviations) used within the scope of
the different Papers of this thesis.
Abbreviation Name
Scanning electron
SEM/EDS
microscopy/ Energy
(-mapping)
dispersive x-ray analysis
Environmental scanning
ESEM/EDS electron microscopy/Energy
dispersive x-ray analysis
Focused ion beam-scanning
FIB-SEM
electron microscopy
(In-situ) (In-situ) Infrared reflection
IRAS absorption spectroscopy
Confocal Raman micro-
CRM
spectroscopy
Grazing incidence
GIXRD
x-ray diffraction
Scanning Kelvin probe
SKPFM
force microscopy
X-ray photoelectron
XPS/AES spectroscopy/ Auger
Electron spectroscopy
Glow discharge optical
GDOES
emission spectroscopy
Optical microscopy /
OM
Stereomicroscopy
Atomic absorption
AAS
spectroscopy
Atomic emission
AESEC
spectroelectrochemistry
Used in
Main information
Papers
Corrosion product
morphology/ elemental, I-V
compositional distribution
In-situ corrosion product
morphology/ elemental II
distribution
Milling of trenches to visualize
III
analyzed surface area
(In-situ) Functional groups I, II, IV, V
Lateral distribution of
I-V
functional groups
Crystalline phases I, II, IV, V
Surface topography and Volta
III
potential mapping
Elemental composition and
I, IV
chemical state information
Elemental depth distribution IV
Surface morphology IV
Release of metals I, IV
In-situ release of metals I

17
 
3.1 Scanning electron microscopy with x-ray microanalysis
(SEM/EDS)
Scanning electron microscopy (SEM) is a kind of electron microscope that
generates images by scanning the sample by means of a focused beam of electrons.
When an electron beam strikes onto a material, accelerated electrons can undergo
elastic and inelastic scattering. This results in various signal emissions that depend on
the incident energy of the electron beam [121, 122]. Typical signals include secondary
electrons (SE), backscattered electrons (BSE), Auger electrons and x-rays. The
electron scattering and photon- and x-ray-production develops in a volume, the
electron interaction volume, within the material where interactions occur by
impinging accelerated electrons, schematically illustrated in Fig.3.1 [123]. The spatial
resolution depends on the generated interaction volume of the emitted energy. Several
interactions of these signals are utilized for imaging, quantitative and semi-
quantitative investigations of materials.

Figure 3.1. Interaction volumes for different electron-sample interactions [123].

Secondary electrons and backscattered electrons for sample imaging, and

characteristic x-rays are the most commonly used signals for compositional analysis.

18
 Secondary electrons that are emitted from the atoms occupying the top surface are
useful to gain morphological and topographical information. Backscattered electrons
are incident electrons which are scattered by the atoms in the solid. Therefore the
contrast of the image indicates differences in average elemental composition. A SEM
image is generated when the electron beam is scanned in a raster scan pattern and the
beam position is combined with the detected signal [122].
The interaction of the electron beam with atoms in the sample contributes to the
shell transitions, and the energy difference between the two shells may be released in
the form of an x-ray. Energy dispersive x-ray spectroscopy (EDS) allows elemental
compositional analyses of the surface, facilitated by the detection and measurement
of the energy of the x-rays that are characteristic of the atomic structure of the element
from which they were emitted [123]. EDS provides rapid qualitative or quantitative
elemental information and is able to generate elemental maps and line profiles.
High resolution images were generated by means of a FEG-SEM instrument, a
LEO 1530 field emission gun SEM with a Gemini column, upgraded to a Zeiss Supra
55 column (equivalent). An accelerated voltage of 15kV and an aperture size of 60
µm were used to record the images. Elemental distribution information was obtained
by means of an EDS X-Max SDD (silicon drift detector) 50 mm2 detector from Oxford
Instruments.
A table-top SEM instrument (Hitachi TM-1000) equipped with a Hitachi EDS
facility was also utilized to analyse the surface morphology and provide compositional
information, using an accelerating voltage of 15 kV.
3.1.1 Environmental - SEM (ESEM)
An environmental scanning electron microscopy (ESEM) is a SEM that permits
examination at near atmospheric pressures unlike conventional SEM, which operates
in vacuum. The ESEM allows high resolution imaging of wet or dry, insulating or
conducting samples, and allows in-situ analysis at specific environments generated
within the chamber. The ESEM system utilizes differential pump systems and
specialized electron detectors that permit electron beam transfer from the high vacuum
of the column to the high pressure in the chamber [121]. A state of art ESEM can
generate electron micrographs at pressures as high as 50 Torr, and at temperatures as
high as 1000 °C, which makes it a unique instrument to image realistic surface
conditions [124].
In-situ analyses were performed using a FEI-XL 30 Series ESEM instrument. The
acquired relative humidity (RH) was obtained by controlling the temperature and
pressure by means of a thermoelectric stage controller. Images were generated using
a gaseous secondary electron (GSE) detector in the environmental mode.

19
 
 Ex-situ measurements were also carried out by means of the normal SE/ BSE
detector. All images (75% SE and 25 % BSE) were collected using an accelerating
voltage of 15, 20 or 30 kV at high vacuum conditions. Elemental analysis and mapping
were performed using an EDAX Phoenix EDS system with an ultra-thin window Si-
Li detector.
3.1.2 Focused ion beam - SEM (FIB-SEM)
A focused ion beam-scanning electron microscope (FIB-SEM) is a SEM equipped
with a FIB system. A finely focused beam of usually gallium ions can be operated at
low beam currents for imaging or high beam currents for sputtering or milling in local
areas [125]. In a FIB-SEM system is both the electron column and the ion column
embedded in the same chamber and focused at the same spot at the sample surface
[126]
.
FIB milling was accomplished by using a Quanta 3D instrument from FEI with a
Ga+ ion source, which operated at an acceleration voltage of 30 kV and ion probe
currents of 30 nA. A selected 5050 μm area was marked as the area of interest for
surface analysis by framing two trenches, each sized 5015μm and with a depth of 5
μm.

3.2 Infrared reflection absorption spectroscopy (IRAS)

Infrared spectroscopy is a vibrational technique used to identify the presence of
functional surface groups based on their specific frequencies that are characteristic of
their structures. The technique can be used for several types of samples including
solids, liquids and gases. IR spectroscopy mostly investigates the interaction between
an external electromagnetic field and a dipole from the vibration of a molecule [6].
When irradiated with infrared light (photons), a sample can absorb the incident
radiation. This excites molecules into a higher-energy vibrational state, resulting in a
change in dipole moment [10, 127]. The process takes place when the photon energy
corresponds to the energy difference between two vibrational states.
The main selection rule in IR spectroscopy is required for the molecular vibration
being infrared active, i.e. during a vibration should the dipole moment (μ) change with
respect to the normal coordinate (Q), normally described as:

Fourier transform infrared (FTIR) spectrometry is a commercial technique that

allows infrared spectra to be recorded using an interferometer for which the intensity
of each wavelength of light at a different audio frequency could be modulated [127].

20
 Infrared reflection absorption spectroscopy (IRAS) is an IR technique based on
reflection, suitable for investigations of thin films on e.g. metal surfaces.
Measurements of a single external reflection at near-grazing incidence angle enable
adsorbed monolayers on metal surfaces to be detected. Only those dipole transition
moments of adsorbed molecules perpendicular to the surface are observed by means
of p-polarised light [6]. IRAS provides information on the molecular vibrations in the
surface film from which surface species can be identified [128]. This information is
collected as the peak absorbance, presented in the unit of (-log (R/R0)), where R is the
reflectance of the exposed sample surface and R0 the reflectance of the non-exposed
sample, used as background [55].
IRAS analyses were performed using a commercial Digilab 4.0 Pro FTIR
spectrometer, equipped with a mercury cadmium telluride (MCT) detector. The p-
polarized infrared beam strikes the sample surface at a grazing angle of around 78°,
are reflected into the nitrogen cooled MCT detector via the CdTe window of an
external chamber and recorded. The set-up is schematically displayed in Fig.3.2.
IRAS spectra can be difficult to obtain for conditions when the surface patina is too
rough or thick. FTIR measurements were then employed using a Thermo Nicolet 6700
FTIR spectrometer equipped with a Deuterated triglycine sulfate (DTGS) detector.
FTIR spectra were generated from powder scraped from the surface.

Figure 3.2. The experimental chamber used for IRAS experiments. (Cited with permission
from Dr. Aastrup from Fig. 2. in ref. [55])

In-situ IRAS analyses of samples with or without pre-deposited NaCl were

performed in a chamber inside the Digilab 4.0 Pro FTIR spectrometer with humidified
air following the wet/dry cycles, schematically displayed in Fig.2.1. Controlled
humidified conditions were obtained by mixing dry and wet pre-cleaned compressed

21
 
air of reduced CO2 (lower than 20 ppm), for exposures of Galfan samples in the
experimental chamber, shown in Fig.3.2. In order to obtain ambient CO2
concentrations (350 ppm) for exposure conditions of Cu sheet and the Cu-based
alloys, a small flow of air with 1.17% CO2 from a CO2 cylinder was added into the
humidity chamber. In-situ IRAS spectra of formed corrosion products were generated
during the dry cycles. All spectra presented in this thesis were collected acquiring
1024 scans with a resolution of 4 cm-1.

3.3 Confocal Raman micro-spectroscopy (CRM)

Raman spectroscopy is another technique used to obtain vibrational spectra, similar
to infrared spectroscopy, however with different mechanisms and selection rules. The
Raman effect, a form of inelastic scattering, means that the molecules are excited from
their ground state to a virtual energy state by an incident photon with an energy
significantly larger than the vibrational transition. A new photon is scattered from the
virtual state when the molecule relaxes and it returns to a different rotational or
vibrational state [127]. The energy difference between the original and new states results
in a shift in frequency of the scattered photon away from the excitation wavelength.

Figure.3.3. IR absorption, Rayleigh, stokes and anti-Stokes Raman scattering processes. υ0

and υ1 represent the vibrational ground state and the first excited state, respectively, ΔEv is
the energy difference between the vibrational states, hv represents the energy of incident
photons, and Ev the energy of scattered photons [128].

There are three kinds of scattering phenomena: Rayleigh, Stoke and anti-Stoke
scattering, schematically illustrated in Fig.3.3, and compared with normal infrared
adsorption. In Rayleigh scattering are photons elastically scattered, which results in

22
the same energy as the incident photons [128]. A Stoke scattering process means that
the scattered photon shifts to a lower frequency when the final vibrational state is
higher in energy than the initial state. Anti-Stoke scattering occurs when the final
vibrational state is lower in energy than the initial state, and the scattered photon shifts
to a higher frequency.
The absorption band position in IR spectroscopy depends on the absolute frequency
of the incoming photons whereas the band positions in Raman spectroscopy rather are
related to the difference in frequency between excited and scattered photons [128].
Different from infrared spectroscopy where the selection rule is determined by the
dipole moment during a vibration, the selection criteria depend on the polarizability
(α):

Confocal Raman micro-spectroscopy (CRM) is Raman spectroscopy combined

with confocal microscope. When the laser light strikes the sample surface through a
microscope setup, the excited laser light is filtered to reach the detection system in the
focal plane. Only signals from the image plane are collected by the confocal optical
system, contributing to a high lateral resolution [129]. Chemical analysis can be
conducted by means of CRM if used combined with parallel vibrational information
[6]
.
CRM analyses were performed by utilizing a WITec alpha 300 system, equipped
with a laser source of wavelength 532 nm. A Nikon objective 100, Nikon NA0.9 NGC,
and a pinhole of 100 µm diameter were used for the measurements. Raman spectra
were generated within the scanned area with lateral and vertical resolutions of
approximately 300 nm and 2 μm, respectively, and an integration time of 50 ms for
each Raman spectrum.

3.4 Grazing incidence x-ray diffraction (GIXRD)

X-ray diffraction (XRD) is an analytical technique able to identify crystalline
phases and to provide information on unit cell dimensions of a material. A
monochromatic x-ray irradiates a crystalline material that produces diffracted x-rays
at various angles, according to Bragg’ law [130]. This law connects the wavelength of
the primary beam (λ), the angle of diffraction (θ) and the lattice spacing in a crystalline
sample (d):
nλ = 2d sinθ

23
 
 The crystalline phases are identified either directly via observed 2θ positions, or
recalculated into d-spacings and compared with standard reference patterns [127].
Grazing incidence x-ray diffraction (GIXRD) uses small incident angles for the
incoming x-rays, which significantly increase the path travelled by the x-rays. The
small incidence angle makes diffraction surface sensitive, and obtains information
primarily from the thin film or surface layers, unlike normal XRD which typically
collects bulk information [131].
GIXRD analyses were carried out by means of an X’pert PRO PANALYTICAL
system, equipped with an x-ray mirror (CuKα or MoKα radiation) and a 0.27° parallel
plate collimator on the diffracted side. The scanned area was 11 cm at a grazing
angle of 88º versus the surface.

3.5 Scanning Kelvin probe force microscopy (SKPFM)

Scanning Kelvin probe force microscopy (SKPFM) is a variant type of atomic force
microscope (AFM), widespread used to study the electrical properties of metal
surfaces. SKPFM measures the work function difference at atomic or molecular
scales, determined by electrostatic forces between a conductive AFM tip and the
sample. The work function represents the difference between the Fermi level and the
vacuum level for each material. If two materials are brought in contact, a net electric
current flows between them until they reach the same Fermi level [132]. A voltage is
applied between the tip, which acts as a reference electrode that forms a capacitor with
the surface, and the sample in order to measure the difference in work function,
denoted the Volta potential or contact potential difference. The normal topographic
scan methods in AFM can be used independently, thereby the topography and Volta
potential mapping can be determined simultaneously on the same surface area [133, 134].
SKPFM is a local probing technique useful for characterization of the corrosion
processes associated with local inhomogeneities on metal surfaces [97]. To some
extent, the relative nobility of microstructural features or phases of alloys, which is
significantly related to microgalvanic interactions, can be suggested based on the
Volta potential findings [98, 99]. However, interpretations must be made with caution as
the technique measures absolute surface potentials on polished surfaces, which is
possibly different from the real surface characteristics.
SKPFM measurements were employed using an Agilent 5500 scanning probe
microscope equipped with a MAC III unit in single-pass mode, and a Nanoscope IV
AFM with facilities for Volta potential measurements in two-pass mode. The probe
was PtIr-coated Si, supplied by Bruker, with a nominal spring constant of 1-5 N/m
and a resonance frequency of 60-100 kHz.

24
3.6 X-ray photoelectron spectroscopy/ Auger electron spectroscopy
(XPS/AES)
X-ray photoelectron spectroscopy (XPS) is a powerful technique used for
elemental analysis and interpretation of oxidation states of the outmost surface layers
(5-10 nm). By irradiating a surface with a beam of x-rays, electrons with binding
energies lower than the excitation beam can be ejected. XPS spectra are obtained
while measuring the kinetic energy and analyzing the number of escaped electrons
from the material simultaneously [135].
Auger electron spectroscopy (AES) is another surface sensitive technique used for
analysis of elements and oxidation states of the outmost surface layers. When a
primary beam strikes on a sample surface, the Auger process results in the emission
of secondary electrons from excited atoms. Information for elemental identification
and quantification is obtained via of the kinetic energy and intensity of generated
Auger peaks [127].
XPS measurements were performed with a Kratos AXIS UltraDLD x-ray
photoelectron spectrometer (Kratos Analytical, Manchester, UK) system combined
with an Auger unit. A monochromatic Al x-ray source (1486.6 eV) operated at 300 W
(15 kV/20 mA) was used during the measurements. The analysis area was
approximately 1 mm2 (most of the signal from a 700300 µm surface area). Wide
spectra and detailed high resolution spectra (pass energy: 20 eV) were collected. AES
mapping was generated using an acceleration voltage of 10 kV and a beam current of
300 nA.

3.7 Glow discharge optical emission spectroscopy (GDOES)

Glow discharge optical emission spectrometry (GDOES) is widely used for
elemental analysis and in-depth profiles on solid conductive materials. The sample is
etched by cathodic sputtering in a glow discharge source. Sputtered atoms are excited
by an argon plasma into which characteristic photons are emitted and collected by
photomultipliers [136].
GDOES analyses were made using a Leco GDS 850 instrument. By using Ar
plasma at a potential of 700 V and a current of 20 mA, a circular area with a diameter
of 4 mm was continuously sputtered. The Ar pressure varied between 6 and 7.5 Torr.

25
 
3.8 Optical microscopy (OM)/ Stereomicroscopy
Optical microscopy is a fundamental technique for image magnification of samples
by using visible light and a system of lenses. With help of normal light-sensitive
cameras, the generated magnified images can be captured [121]. Stereomicroscopy uses
light reflected from the sample surface instead of transmitted light which enables a
three-dimensional visualization of the surface.
Optical microscopy imaging was employed to investigate surface morphological
changes by using a Leica DM 2700M microscope that combines high-quality Leica
optics with state-of-the-art universal white light LED illumination.
Stereomicroscopy imaging was performed to document the surface appearance by
means of a M205C Stereo microscope with a Leica DFC 290 video camera, using a
D65 reference light source applied at 10° at a magnification of 40×.

3.9 Atomic absorption spectroscopy (AAS)

Atomic absorption spectroscopy (AAS) is an analytical technique that
quantitatively determines elements in solution. By absorbing an optical radiation
(light) of a given wavelength, the electrons of the free atoms in the gaseous state in
the atomizer can be transited to higher energy levels [137]. This defined quantity of
energy (wavelength) is measured as photons of light transmitted by the sample, which
is specific to a particular electron transition in a particular element. By comparing this
wavelength to the wavelengths which originally passed through the sample, the total
concentration of a specific element can be obtained [127].
Standards of known concentration for the element of interest are necessary to
establish the connection between the measured absorbance and the element
concentration of interest, therefore relying on the Beer-Lambert Law. This law
connects the absorbance (A) proportional to the wavelength-dependent molar
absorptivity coefficient (ε), the path length of the sample (b) and the concentration of
the compound in solution (c):
A = εbc
All metal runoff measurements were conducted by means of AAS using a Perkin
Elmer AAnalyst 800 instrument. Analyses of released zinc were performed using the
flame mode AAS, whereas released concentrations of aluminum were determined
with graphite furnace AAS (GF-AAS) due to low concentrations (sub-µg/L). Prior to
analysis, the runoff water was acidified to a pH less than 2 to ensure complete
dissolution of potentially formed complexes. Three replicate readings were made for

26
each sample and control samples (every 10th sample), successively measured during
the analysis.

3.10 Atomic emission spectroelectrochemistry (AESEC)

Atomic emission spectroelectrochemistry (AESEC) is a novel instrument that
combines inductively coupled plasma optical emission spectrometry (ICP-OES) [107]
downstream an electrochemical flow cell. Real-time measurements of released metals
as a function of time can be achieved, both at open circuit potential (OCP) conditions
and at applied potentials [138]. Details regarding AESEC is given elsewhere [107].
Emission signals from the ICP-OES and the open circuit potential were constantly
measured and recorded after averaging over a user defined integration period. Release
rates of metals were calculated based on the measured metal concentrations, Cm, times
the flow rate per surface area. Metal concentrations were determined using a
polychromator of Ultima 2C Horiba JobinYvon ICP-OES spectrometer (focal
distance 50 cm), using wavelength 213.85 nm (Zn) and 167.08 nm (Al). All
electrochemical experiments were carried out using a potentiostat (EG&G Princeton
Applied Electronics M273A) functioning in potentiostatic mode in connection with
ICP-OES. All AESEC measurements were performed by colleagues at Ecole
Nationale Supérieure de Chimie de Paris, France.

27
 
4 Influence of microstructure on corrosion initiation

4.1 The eutectic structure of Galfan consists of an η-Zn matrix and β-Al
lamellas and rods of lower surface nobility compared with the matrix, and are
separated by β-Al grain boundaries in which ZnO and Al2O3 preferentially
form. (Paper III)

The selected eutectic area was easily identified via FIB-milled trenches on a
diamond polished Galfan surface, displayed in Fig.4.1a. Surface analyses were carried
out on the very same surface area (3232 μm) by utilizing SEM/EDS-mapping for
morphology and elemental composition analyses, SKPFM for surface topogragphy
and Volta potential, and CRM to obtain information of lateral differences in surface
oxide composition.

Figure 4.1. SEM images of trenches milled by FIB on a diamond polished Galfan surface
(a), the selected surface area (3232 µm) between the trenches (b), and the corresponding
EDS-mapping images of elemental distribution of zinc (c) and aluminum (d).(Paper III)

28
 The microstructure of the selected surface area between the trenches is shown in
Fig.4.1b, and the corresponding elemental distribution, as obtained by EDS-mapping,
in Fig.4.1c (zinc) and Fig.4.1d (aluminum), respectively. The structure of the eutectic
area consists of a zinc-rich η-Zn matrix (<5wt-% Al/(Al+Zn)) and aluminum-rich β-
Al lamellas or rods (Al/(Al+Zn) >5 wt-%), separated by β-Al grain boundaries
(Al/(Al+Zn) >10 wt-%). It has been reported that the grain boundaries form during
the coarsening process of the β-Al phase precipitation in the η-Zn phase, which is
more pronounced at higher temperature and annealing time upon production [34].
Complementary measurements by SKPFM were conducted on the same surface
area. The AFM-image (Fig.4.2a) displays a relatively flat topography whereas some
parts of the grain boundaries show a lower height than the surrounding matrix. The
corresponding SKPFM-image (Fig.4.2b) displays that the β-Al areas exhibit lower
Volta potential than the matrix, indicating a lower relative nobility of the β-Al
lamellas/ rods. They are therefore possibly more susceptible to corrosion initiation
compared with surrounding η-Zn areas [97]. The β-Al grain boundaries exhibit a
strongly varying Volta potential, alternatively, lower Volta potential at some areas
and higher at other areas than the surrounding. These variations seem to some degree
related to variations in topography along the grain boundaries.

Figure 4.2. AFM-based topography (a) and Volta potential mapping (b) obtained with
SKPFM of the same Galfan surface area (3232 µm) as in Fig.3.1. (Paper III)

Evident residues of thicker films of Al2O3 and ZnO, especially along the β-Al grain
boundaries [139], were locally observed by means of CRM even after diamond-
polishing. This is most likely a result of oxides formed during the high temperature
manufacturing process.
A lower Volta potential of the β-Al lamellas or rods compared with the surrounding
η-Zn matrix is expected from a thermodynamic perspective, and indicates that the
origin of the Volta potential variation predominantly is due to variations in bulk

29
 
composition between different phases in the microstructure. It suggests furthermore
that layers of Al2O3 and ZnO, expected to form at the surface besides in the grain
boundaries, are too thin to influence the Volta potential difference as determined by
SKPFM. This conclusion is contradictory to findings for Galvalume coatings (Zn-
55wt% Al) of high aluminum content, where the continuous and thick aluminum
oxide significantly enhances the Volta potential, in particularly in areas of aluminum-
rich dendrites [14].

4.2 Corrosion initiation observed for Galfan in the zinc-richer η-Zn phase
adjacent to the less zinc-rich β-Al phase. Both carbonate and chloride-
containing phases are formed in humidified air and in the presence of NaCl.
(Paper II)

The gradual deliquescence of pre-deposited NaCl particles (4 μg/cm2) on Galfan

were observed by ESEM at in-situ conditions. Subsequent wet/dry cyclic exposures
of Galfan, pre-deposited with 4 μg/cm2 NaCl, were performed, and the corrosion
products were analyzed by means of SEM and in-situ IRAS. Generated findings on
the corrosion product formation were compared with findings for Galfan exposed to
short and long-term outdoor marine exposure conditions.

Figure 4.3. ESEM images of a Galfan surface pre-deposited with 4 μg/cm2 NaCl particles
and exposed to increasing relative humidities (RH). (a) 0% RH; (b) 40% RH; (c) 70% RH
and (d) 90% RH. (Paper II)

30
 Figure 4.3a shows the distribution of individual micrometer-sized NaCl crystals
pre-deposited on a Galfan surface at high vacuum conditions. Figure 4.3b, obtained at
40% RH, displays how the NaCl crystals seem to slightly change in shape and in some
cases also increase in size. At 70% RH, close to the point of deliquescence of NaCl,
the crystals completely turned into droplets, Fig.4.3c. At 90%RH, the NaCl droplets
further spread, probably due to secondary spreading effects [12], and gradually covered
most of the surface, Fig.4.3d.
Figure 4.4a displays the same Galfan surface as shown in Fig.4.3 after exposure to
one wet/dry cycle at 90% RH. Figure 4.4b reveals a selected area in Fig.4.4a at higher
magnification and shows a high frequency of small granular corrosion products,
primarily formed in the η-Zn phase between areas of the β-Al phase. After the
exposure to two wet/dry cycles, Fig.4.4c, corrosion products of relatively uniform
thickness completely covered the surface, whereas clusters of signficantly thicker
corrosion products formed in some areas, Fig.4.4d. EDS analysis revealed Zn, Al, O
and Cl to be the main elements of these clusters.

Figure 4.4. SEM images of a Galfan surface pre-deposited with 4 μg/cm2 NaCl particles and
exposed to wet/dry cycles at 90% RH. (a) the same surface as in Fig.4.3 after 1 wet/dry cycle
exposure at 90% RH; (b) a magnification of a specific corroded area observed in (a); (c)
corrosion products formed after 2 wet/dry cycles, and (d) a chloride-rich corrosion product
cluster after 2 wet/dry cycles. (Paper II)

31
 
 The corresponding in-situ IRAS spectra were obtained after one (lower curve) and
two (upper curve) wet/dry cycles, displayed in Fig.4.5. Several peaks were observed
upon exposure with pre-deposited NaCl, including the peaks assigned to ZnAl2O4 at
560-670 cm-1, the peak tentatively assigned to OH- in Zn(OH)2 or Al(OH)3 at 1143
cm-1 [18, 140, 141] and the major peak at 1370 cm-1 identified as CO32- in
Zn6Al2(OH)16CO3·4H2O [66]. Three major peaks in the range from 700 to 1100 cm-1
were assigned for Zn -O-H and Al-O-H vibrations, possible evidence for the formation
of a layered double hydroxide such as Zn2Al(OH)6Cl·2H2O [142] and/or
Zn5(OH)8Cl2·H2O [18]. However, it was not possible to distinguish these phases from
each other.

Figure 4.5. In-situ IRAS spectra obtained on Galfan after exposure for 1(a) and 2 (b) wet/dry
cycles at 90% RH pre-deposited with 4 μg/cm2 NaCl. (Paper II)

The rounded shape of most NaCl droplets observed with ESEM under in-situ
conditions, Fig.4.3d, indicates that the wetting process was the same along the whole
Galfan surface, regardless of the microstructural features. In addition, when analyzing
the same corroded surface with SEM under vacuum conditions, Fig.4.4a, the circular
features that stand for the droplets in Fig.4.3d seem to cover parts of the Galfan surface,
independent of the grains and phases beneath. However, when studying a corroded
area at higher magnification, Fig.4.4b, visible granular corrosion products of larger
size and occurrence were primarily observed in the η-Zn phase between areas of the
β-Al phase. Due to its slightly higher Al-content, the β-Al phase could be expected to
be more susceptible for corrosion initiation. However, oxide formation seems to
inverse these conditions so that the β-Al phase acts more passive than η-Zn phase
during the exposures. Local clusters of corrosion products shown in Fig.4.4d, were by

32
IRAS shown to be either composed of Zn2Al(OH)6Cl·2H2O and/or Zn5(OH)8Cl2·H2O.
The IRAS-spectra furthermore revealed the formation of Zn6Al2(OH)16CO3·4H2O,
another layered double hydroxide predominantly formed upon exposure without pre-
deposited NaCl [143].
Similar corrosion product morphologies were observed by SEM on Galfan surfaces
after short term (2 and 4 weeks) marine exposures, Fig.4.6, as after the laboratory
exposures, Fig.4.4. Corrosion was preferentially initiated in the η-Zn phase and
developed into clusters of corrosion products, Fig.4.6c. These cluster-like corrosion
products mainly contained Zn, Al, O and C, as evidenced by EDS-analysis, and may
be attributed to ZnO or Zn6Al2(OH)16CO3·4H2O. Different sheet-like corrosion
products were observed after two weeks, Fig.4.6d, and after four weeks, Fig.4.6d.
These corrosion products contained significant amounts of Cl, beside Al, Zn and O,
and consisted possibly of chloride-rich corrosion products, such as
NaZn4Cl(OH)6SO4·6H2O, Zn2Al(OH)6Cl·2H2O and/or Zn5(OH)8Cl2·H2O [144].

Figure 4.6. (a) SEM image of corrosion products on Galfan exposed for 2 weeks at the
marine site of Brest, France; (b) a selected area of (a) at higher magnification; (c) carbonate-
rich corrosion products after 2 weeks, and (d) chloride-rich corrosion products after 4 weeks.
(Paper II)

33
 
4.3 Selective zinc release and corrosion initiation in the zinc-rich phase
observed for Galvalume in chloride containing media. Long-term correlation
observed between the released zinc fraction and the surface coverage of zinc
and aluminum-rich corrosion products. (Paper I)

Short-term metal release from Galvalume and the formation of corrosion products
were investigated when exposed to synthetic rainwater and seawater by means of two
different set-ups, immersion tests and flow-cell tests at OCP conditions. The relevance
of generated results obtained at given laboratory conditions were validated with
findings from long-term atmospheric outdoor exposures.
Fig.4.7a presents release rates of zinc and aluminum from Galvalume after
immersion tests determined by means of AAS. Zinc was primarily released compared
with aluminum, independent of test media. Observed differences in zinc release rates
were small up to 1800s, but were significant (factor of two) after 3000 s of exposure
in seawater, containing significantly more chloride but of a more alkaline pH
compared with rainwater. These results indicate that the protective ability of
aluminum oxide was locally destroyed by chloride ions after a certain time period, a
process that took place in a faster rate in seawater compared with rainwater,
respectively. However, observed release rates of aluminum were for most conditions
very low, being below or close to the limit of detection. Similar to findings of the
immersion tests were significantly higher release rates of zinc compared to aluminum
observed for all media in the flow cell test at OCP conditions, as illustrated in Fig.4.7b
for seawater. Preferential release of zinc was evident in both synthetic rainwater and
in seawater.

Figure 4.7. Release rates of zinc and aluminum from Galvalume during immersion tests (a)
in rainwater and seawater, respectively, and during flow-cell tests (b) in seawater. (Paper I)

34
 Corrosion products of relatively similar surface morphology were formed on
Galvalume upon immersion and flow cell tests at OCP conditions, Fig.4.8. Consistent
with literature findings [6-8], were corrosion products preferentially formed in zinc-rich
interdendritic areas, an effect particularly pronounced upon seawater exposure. Minor
morphological differences were observed between samples exposed to the rainwater
media of different chloride content, suggesting only slight and locally occurring
corrosion. Al2O3 was identified as the only crystalline corrosion product by means of
GIXRD at all exposure conditions, an oxide that, according to literature findings [14],
is favoured by the presence of chlorides.

Figure 4.8. SEM images of Galvalume during immersion tests for 3000 s in artificial rain
water ((a) 0.01 mM and (b) 0.3 mM Cl- ), and (c) in artificial sea water (560 mM Cl-) and
during flow-cell tests in artificial sea water (d). The average mass ratio Al/ (Al+Zn) refers
to XPS compositional measurements of two separate areas (each sized 0.4 mm2). (Paper I)

The dominance of a thin layer of Al2O3 was clearly demonstrated by means of XPS,
showing a Al/(Al+Zn) mass ratio varying between 0.85 and 0.99 in the outermost
surface layer of non-exposed bare Galvalume. Al2O3 forms at high temperatures
during alloy production and was present on both zinc-rich and on aluminum-rich
areas. Exposure in artificial rainwater during the immersion tests resulted in relatively
small changes of the Al/(Al+Zn) surface mass ratio at 0.01 mM Cl- (mean ratio: 0.96)

35
 
and 0.3 mM Cl- (mean ratio: 0.84). Exposures in seawater resulted on the other hand
in significant changes in surface distribution between aluminum-rich and zinc-rich
corrosion products, elucidated by a reduced mean Al/(Al+Zn) surface mass fraction
to 0.63 (0.58-0.68) after the immersion test, and to 0.23 after the flow-cell test.
Furthermore, an IRAS peak was identified at around 1467 cm-1, assigned to CO32-,
possibly associated with Zn6Al2(OH)16CO3·4H2O and/or Zn5(OH)6(CO3)2.
Findings of the relative surface distribution of aluminum- and zinc-rich corrosion
products were in agreement with observed metal release data showing increased
release rates of zinc with time, and a more rapid release rate in seawater after the
longest period investigated (3000 s) for both experimental set-ups. This can
tentatively be explained by a faster interaction and local destruction of the aluminum
oxide by the high chloride content in seawater compared with artificial rainwater.
Both sulfate and chloride were observed by means of XPS/AES on Galvalume
surfaces exposed to seawater conditions. According to literature findings may sulfate
be associated to the local formation of basic zinc sulfates and or chlorides in zinc-rich
interdendritic areas under atmospheric conditions [35, 36, 60, 68, 145].

Figure 4.9. Average release rates of zinc and aluminum (a) and corresponding annual
release Al/(Al+Zn) ratio for each year of exposure (b) for Galvalume exposed to unsheltered
conditions at the marine site of Brest, France for five years. (Paper I)

Release rates of zinc and aluminum were continuously monitored for Galvalume
surfaces exposed at unsheltered conditions for 5 years in a marine environment[14].
Observed release rates obtained under laboratory conditions revealed the same trend
as observed at field conditions. Significantly more zinc was released compared with
aluminum throughout the exposure period, Fig.4.9a, with an annual Al/ (Al+Zn)
release ratio varying within 0.04±0.01 for individual years of exposure, Fig.4.9b. Field
data revealed, similar to laboratory findings, a preferential release of zinc with
increased rates during the first year of exposure, Fig.4.9a. Al2O3 was predominantly

36
present over the entire Galvalume surface before exposure, and was subject to local
destruction upon interaction with chloride ions during exposure. Gradual formation
of zinc-rich corrosion products, most likely non-crystalline basic zinc chlorides and/or
sulfates, was preferentially taking place in the zinc-rich interdendritic phases. This
resulted in gradually increased release rates of zinc during the first year of exposure.
However, due to the gradual formation and integration of aluminum rich corrosion
products also in zinc-rich interdendritic areas [14], reduced release rates of zinc were
observed with time during the 5 year exposure.

4.4 The dual-phase structure of Cu40Zn consists of zinc-richer β-phase

crystals of lower surface nobility than the α-phase. Corrosion initiation is
observed in the β-phase at low pre-deposition of NaCl. (non-published data)

A dual-phase brass alloy, Cu40Zn, was introduced to explore the influence of

microstructure on corrosion initiation. Prior to exposure was the alloy surface
analyzed by means of optical microscopy (OM) to gain metallographic information,
SEM/EDS for morphology and elemental compositional analyses, and SKPFM to
assess surface topography and to map differences in Volta potential over the surface.
The surfaces were pre-deposited with 0.1 μg/cm2 NaCl and subsequently exposed to
wet/dry cycles. Corrosion initation was primarily analyzed by means of CRM.

Figure 4.10. Images showing the microstructure of an unexposed Cu40Zn surface by optical
microscopy (a), and by SEM after etching (2M HCl+ 0.2M FeCl3) for 15 s to reveal the alloy
microstructure (b).

The microstructure of the diamond-polished Cu40Zn surface is shown in Fig.4.10a,

as viewed by OM. The dual-phase structure consists of β-phase irregular grains
typically sized from 5 to 20 µm in an α-phase matrix, and result from the solidification
processes during casting [43]. A SEM image of the etched surface further reveals the
α-β dual phase characteristics, Fig.4.10b. The β-phase exhibits a platelet-type

37
 
morphology and occurs in different grains with an estimtated surface coverage
fraction of approximately 10%. Elemental compositional EDS analysis revealed a
more zinc-rich β-phase (42-46 wt-% Zn/(Zn+Cu)) compared with the α-phase (37-41
wt-% Zn/(Zn+Cu)). The α-phase solidifies firstly during the cooling process and
obtains hence a higher Zn-content, compared with the subsequent solidification of the
β-phase of lower zinc content [43]. The SEM/EDS investigation revealed further the
presence of granular sulfur-rich inclusions (0.5-10% wt-% S/(S+Zn+Cu)). Inclusions
with a high content of sulfur (5-10% wt-% S/(S+Zn+Cu)) were associated with a
higher content of zinc compared with adjacent surface areas, and indicate a chemical
composition similar to ZnS [110].

Figure 4.11. AFM-based topography (a) and Volta potential mappings (b) obtained with
SKPFM of an unexposed diamond polished Cu40Zn surface.

Figure 4.12. Optical image (a) and combined Raman mapping images (b, c) obtained with
CRM of the squared-sized area in (a). Raman map of Cu2O ((b), integrated between 150 and
250 cm-1) and of ZnO ((c), integrated between 400 and 600 cm-1) in corrosion products
formed on Cu40Zn with pre-deposited NaCl (0.1μg /cm2) after one wet/dry cycle at 90% RH.

Complementary measurements by SKPFM were performed on the diamond-

polished surface observe variations in topography and Volta potential, Fig.4.11. The

38
AFM-image (Fig.4.11a) shows that the β-phase exhibits a lower height than the α-
phase, which may be a result of the polishing process. Grains of the β-phase exhibit a
lower Volta potential compared with the surrounding α-phase, as revealed by the
corrsponding SKPFM-image (Fig.4.11b). This suggests a lower relative nobility of
the more zinc-rich β-phase with possibly a higher susceptibility for corrosion
initiation. Furthermore, a granular area of circular shape of even lower Volta potential
than both the α- and the β-phase was observed with SKPFM (Fig.4.11b). This area
most likely correspond to zinc-enriched sulfur inclusions seen in Fig.4.10a. Their
presence is consistent with previous findings [14, 75, 113].
Figure 4.12a displays the morphology of the Cu40Zn surface pre-deposited with
low amounts of NaCl (0.1 μg /cm2) after exposure to one wet/dry cycle at 90% RH. A
circular darker area appears in the image, which indicates the interaction of a NaCl
droplet with the surface upon deliquescence of deposited NaCl. The slightly zinc-
richer β-phase crystals inside the circular area exhibit a darker feature compared with
the matrix. CRM measurements were conducted on the square-sized area seen in
Fig.4.12a. The results revealed a lateral distribution of cuprite (Cu2O) and of zinc
oxide (ZnO), Fig.4.12b-c. The microstructure evidently influences the initial
formation of corrosion products as Cu2O and ZnO are preferentially formed in the
slightly zinc-richer β-phase grains of lower Volta potential compared with the
surrounding α-phase matrix.
The results are in agreement with recent literature findings [110], in which similar
microstructural effects between grains of slightly different Zn-content could be
observed when a Cu20Zn alloy was exposed to a dilute NaCl solution. It should be
added, however, that this microstructural influence could not be observed when the
same Cu40Zn alloy was exposed to wet/dry conditions with a significantly higher
amount of pre-deposited NaCl (4 μg/cm2). In this case the chloride-induced corrosion
effect seemed to be evenly distributed along the corroded Cu40Zn surface, rather than
preferentially occur in the β-phase.

4.5 Microgalvanic effects on a Cu-Zn patterned sample with pre-deposited

chlorides result in a radial distribution of corrosion products from the Cu
cathode to the Zn anode upon cyclic exposures in humidified air. (non-
published data)

To further explore the effect of structural heterogeneity of CuZn substrates on

chloride-induced atmospheric corrosion a Cu-Zn patterned sample was prepared that
consists of 20 by 20 µm-sized squared Cu-islands regularly deposited on a pure Zn-
substrate, each square at a distance of 20 µm from the next. This Cu-Zn patterned

39
 
sample, from now on designated CuZnP, was pre-deposited with 4μg/cm2 NaCl and
exposed to wet/dry cycles at 90% RH. The lateral distribution and composition of
corrosion products were then analyzed by means of SEM/EDS and CRM, and their
location related to the Cu-Zn surface pattern.

Figure 4.13. SEM images of corrosion products formed on CuZnP pre-deposited with 4μg
/cm2 NaCl and exposed for 1(a) and 6 cycles (b-d) at 90% RH.

Fig. 4.13 reveals the morphology, by means of SEM, of corrosion products formed
on CuZnP after cyclic exposures. After exposure to 1 cycle, relatively uniform
corrosion products preferentially formed on the Zn-matrix surrounding each Cu-
island, Fig.4.13a. After exposure to 6 cycles, a characteristic circular-shaped pattern
of corrosion products formed on the Zn-matrix at a certain distance from the Cu-
islands, Fig.4.13b. At higher magnification (Figs. 4.13c and d) the circular features
are seen as small granular corrosion products, Fig.4.13c, whereas clusters of sheet-
like corrosion products are seen outside the circles, at the center of each of the four
Cu islands seen in Fig.4.13d.
In order to identify the phases in the corrosion products and their location CRM
measurements were performed after exposure to 6 wet/dry cycles, Fig.4.14. CRM
mapping, Fig.4.14b, reveals that cuprite, Cu2O (main peaks at 219, 424 and 636cm-1)

40
[146]
formed on the Cu-island, zinc oxide, ZnO (main peaks for crystalline ZnO at 426
cm and amorphous ZnO at 560 cm-1) [147] on the Zn-matrix, and nantokite, CuCl
-1

(main peaks at 290, 613 and 1110 cm-1) [146] along the boundary in-between. An area
of the Zn-matrix was selected between the four Cu-islands for further CRM-analysis,
Figs.4.14c-d. Besides ZnO and Cu2O, was hydrozincite, Zn5(OH)6(CO3)2 (main peaks
at 386, 1070, 1378, 1586, 2938 and 3450 cm-1) [148, 149] formed close to the periphery
of the circle whereas sheet-like corrosion products of simonkolleite,
Zn5(OH)8Cl2·H2O (main peaks at 270, 400, 910, 2936 and 3486 cm-1) [149-152] formed
outside the circular features at the centre of the four Cu-islands.

Figure 4.14. Optical images ((a) and (c)) and combined Raman mapping images ((b) and
(d)) of corrosion products formed on CuZnP pre-deposited with 4 μg /cm2 NaCl and exposed
during 6 cycles at 90% RH. CRM on Cu2O (blue, integrated between 150 and 250 cm-1),
CuCl (red, integrated between 250 and 350 cm-1), ZnO (yellow, integrated between 400 and
600 cm-1, (e)), the CO32- band in Zn5(OH)6(CO3)2 (cyan, integrated between 1000 and 1100
cm-1, (f)) and the OH band in Zn5(OH)8Cl2·H2O (purple, integrated between 3400 and 3550
cm-1, (g)).

The lateral distribution of corrosion products formed on both Cu and Zn are

believed to be the result of microgalvanic effects between each Cu-island and its
surrounding Zn matrix, and be a result of their relatively large difference in electrode
potential. The circular feature of formed corrosion products and the radial distribution
of corrosion products imply, based on the basic corrosion cell theory, the formation
of a gradient in potential and in chemical composition from each Cu-island (cathodic
area characterized by high local pH and low local chloride concentration in the
aqueous adlayer) to the anodic area in the Zn-matrix, centrally located between the
four Cu-islands (anodic area, low local pH and high local chloride concentration).

41
 
Cu2O is formed on the cathodic Cu-island, CuCl along the Cu/Zn boundary, ZnO and
Zn5(OH)6(CO3)2 on the Zn-matrix closer to the Cu-islands and Zn5(OH)8Cl2·H2O in
the centre of the anodic area that exhibits a high chloride concentration and low pH.
The distribution of corrosion products may be compared with those found by Cole et
al [152, 153], who studied formation of corrosion products on pure zinc beneath a single
NaCl-drop. As a consequence of the radial distribution in potential and local chemistry
in the NaCl-drop, Zn5(OH)6(CO3)2 was found to preferentially precipitate in the
secondary spreading area of the droplet characterized by a higher pH, while
Zn5(OH)8Cl2·H2O formed in the centrally located anodic area, characterized by a
higher chloride ion concentration and lower pH [152, 153].

42
5 Corrosion product evolution and characteristics

5.1 Severe corrosion product flaking observed for Cu and Cu4Sn in chloride-
rich environments is primarily connected to the presence of nantokite. Minor
effects observed for Cu15Zn and Cu5Al5Zn. (Paper V)

The extent of flaking of poorly adherent corrosion products on Cu sheet and three
Cu-based alloys was examined by means of SEM (surfaces and cross-sections). The
hypothesis of flaking being connected with the formation of nantokite was further
elucidated by CRM measurements.

Figure 5.1. Top view SEM images of Cu sheet (a) and Cu4Sn (b) surfaces showing severe
corrosion product flaking, and of Cu15Zn (c) and Cu5Al5Zn (d) surfaces showing minor, or
no flaking. All samples were exposed for 1 year at unsheltered marine field conditions.
(Paper V)

SEM-top view images of the morphology of the patina formed on Cu sheet and the
copper-based alloys (Cu4Sn, Cu15Zn and Cu5Al5Zn) after 1 year at the marine site

43
 
are shown in Fig.5.1. Loosely and heterogeneously adherent corrosion products that
have detached as flakes were observed on both Cu sheet (a) and Cu4Sn (b), while
more adherent corrosion products were evident on both Cu15Zn (c) and Cu5Al5Zn
(d) displaying minor or no flaking at all, respectively. In general, relatively severe
flaking was observed for Cu and Cu4Sn throughout the entire 3 year marine field
exposure, whereas the degree of flaking was only minor for Cu15Zn and no flaking at
all for Cu5Al5Zn during the same time period.

Figure 5.2. SEM images of cross-sections of the corrosion patina formed on Cu sheet (a),
Cu4Sn (b), Cu15Zn (c), and Cu5Al5Zn (d), after 3 years of marine unsheltered field exposure.
(Paper V)

Cross-sectional SEM images of the patina of Cu sheet (a), Cu4Sn (b), Cu15Zn (c)
and Cu5Al5Zn (d) are displayed in Fig.5.2 after 3 years of exposure. In general, the
patina formed on all materials consisted of a two-layer structure, except for Cu4Sn
showing a striped-layer structure. The total average thickness of the patina decreased
according to Cu4Sn ˃ Cu ≈ Cu15Zn ˃ Cu5Al5Zn, a trend remaining during the entire
exposure period. Further EDS line-analyses were conducted on the cross-sections of
all Cu and Cu-based alloys to identify the corresponding elemental distribution. The
patina contained very similar main constituents, and revealed a non-uniform inner
layer primarily composed of Cu and O, probably as cuprite (Cu2O), and a porous outer

44
layer predominantly rich in Cl, besides Cu and O, probably as paratacamite/atacamite,
Cu2(OH)3Cl [71, 79]. In particular, there was an interfacial discontinuous region
enriched with Cu and Cl between the two inner layers of patina on Cu4Sn, Fig.5.2b,
probably attributed to nantokite (CuCl). Literature findings by SEM/EDS have
reported the possible presence of nantokite between the inner layer and the substrate,
or within the outer layer after long term field and/or laboratory exposures [71, 79, 154].
Its presence has also been confirmed by XRD [70-73, 155]. The presence of cuprite (Cu2O)
and paratacamite (or possibly atacamite, Cu2(OH)3Cl) were confirmed by means of
GIXRD.

Figure 5.3. Optical images ((a)-(d)) and combined Raman mapping images (laser source of
532 nm, (e)-(h)) obtained with CRM on Cu2O (blue inner layer, integrated between 150 and
250 cm-1, (i)), CuCl (red intertwined layer, integrated between 250 and 350 cm-1, (j)) and the
OH band in Cu2(OH)3Cl (green outer layer, integrated between 3300 and 3500 cm-1, (k)) of
cross-sections of patina formed on bare Cu sheet, Cu4Sn, Cu15Zn and Cu5Al5Zn exposed at
unsheltered conditions for 3 years at a marine site. (Paper V)

Based on the SEM/EDS findings it was proposed that flaking was related to the
formation of nantokite. This hypothesis was further elucidated by CRM measurements
performed on cross-sections of the patinas formed on bare Cu and Cu-based alloys

45
 
exposed for 3 years at the marine site, displayed in Fig.5.3. The layered structure of
the patina with its main constituents was clearly distinguished by the combined CRM
images. Cuprite, Cu2O (main peaks at 219, 424 and 636 cm-1) [156], was the dominant
constituent of the inner layer, and paratacamite, Cu2(OH)3Cl (main peaks at 373, 519,
930, 977, 3364 and 3447 cm-1) [157] the predominant constituent of the outer layer of
the patina on bare Cu sheet, Cu4Sn, Cu15Zn and Cu5Al5Zn. A discontinuous thin
layer of nantokite was intertwined between the inner and outer layers, supported by
the Raman peak positions characteristic of artificial nantokite, CuCl (main peaks at
290, 613 and 1110 cm-1) [146]. By comparing the CRM images generated for the
different materials, Fig.5.3, it was obvious that the occurrence of nantokite was
significantly more pronounced for Cu sheet and Cu4Sn compared with Cu15Zn
(minor) and Cu5Al5Zn (non-significant). Its presence coincided with the tendency for
corrosion product flaking, which indicates that nantokite plays an important role in
the flaking process.

5.2 Transformation of nantokite to paratacamite results in volume expansion

within the patina causing corrosion product flaking for Cu and Cu4Sn.
(Paper V)

A layer of synthetic nantokite was grown on bare Cu sheet and subsequently

exposed to wet/dry cycles at 90% RH to test the hypothesis that nantokite transforms
at atmospheric conditions to a basic copper chloride. The transformation process was
primarily verified by GIXRD measurements. Different interactions between the NaCl
droplets and the surfaces were elucidated by parallel exposures of the Cu sheet and
the Cu-based alloys, pre-deposited with NaCl (4 µg/cm2), to the same wet/dry
exposures. Formed corrosion products were analyzed by means of SEM/EDS and
CRM.
The synthetic nantokite layer grown on bare Cu sheet was exposed to wet/dry cyclic
conditions in the climatic chamber at 90% RH and subsequently analyzed with
GIXRD. The thickness of the corrosion product layer, determined with a
microprocessor coating thickness gauge, increased continuously from an average
thickness of approximately 10 µm prior to exposure to approximately 50 µm after 14
cycles. In agreement with field exposed samples was the gradual transformation of
artificial nantokite to paratacamite confirmed by GIXRD-analyses, Fig.5.4. It was
evident that this transformation process is associated with a significant volume
expansion, a process that creates internal physical stresses within the patina and
possibilities for subsequent corrosion product flaking [80].

46
Figure 5.4. GIXRD diffraction patterns illustrating the transformation of a synthetic
nantokite (CuCl) layer on bare Cu sheet, pre-deposited with 4 μg/cm2NaCl, to paratacamite
(Cu2(OH)3Cl), after 0 (unexposed), 2 and 14 wet/dry cycles at 90% RH. (Paper V)

Bare Cu sheet, Cu4Sn, Cu15Zn and Cu5AlZn, pre-deposited with NaCl (4 µg/cm2)
were further exposed to wet/dry cycles in the climatic chamber at 90% RH and the
morphology and elemental composition of formed corrosion products were
investigated using SEM/EDS. A few ring-formed corrosion features were present on
Cu sheet and on all Cu-based alloys after 1 cycle (6 h), Figs.5.5a-d, features that were
induced by the spreading of deliquescent NaCl droplets [143]. Whitish small granular
corrosion products revealed a higher content of Cl and O compared with the
surrounding areas. After 14 cycles (7 days) were observed corrosion effects on Cu
sheet and Cu4Sn (Fig. 5.5e and 5.5f) quite severe with a high frequency of granular
corrosion products that almost completely covered the surface, independent of the
original positions of initially formed NaCl droplets. Aggregation of white granular
corrosion products, randomly observed on Cu sheet and Cu4Sn containedmainly Cu,
O and Cl (based on EDS findings). Less severe corrosion effects and ring-like surface
features with more uniformly formed corrosion products were observed on Cu15Zn
and Cu5Al5Zn after 14 cycles (Figs.5.5g and 5.5h) compared with bare Cu sheet and
Cu4Sn.

47
 
Figure 5.5. SEM images of patina formed on bare Cu sheet, Cu4Sn, Cu15Zn and Cu5Al5Zn
pre-deposited with NaCl (4 μg /cm2)and exposed for 1 (a-d) and 14 (e-h) cycles at 90% RH.
(Paper V)

48
 Complementary CRM measurements of local areas (25x25 µm) were conducted on
Cu4Sn after exposures to the wet/dry cycles described above. A ring-like corrosion
feature present after 1 wet/dry cycle was selected for further investigation, Fig.5.6a.
The CRM investigation revealed an evident formation of cuprite surrounding the
periphery of the ring, Fig.5.6f. The characteristic morphology of cuprite followed the
ring-like feature, seen in Fig.5.5b). The formation of cuprite is electrochemically
driven and has been studied in more detail elsewhere [22]. Except for cuprite was
nantokite observed in the ring-like features after 2 cycles (1 day), Figs.5.6b and 5.6g.
Cuprite covered most of the surface while nantokite was preferentially concentrated
along and inside the periphery of the ring. The morphology and distribution of
nantokite with white granular-shaped corrosion products seen in Fig.5.5b, are
consistent with literature findings [80]. After 6 cycles (3 days) was a large part of the
surface covered with circular clusters of nantokite surrounded by cuprite, Figs.5.6c
and 5.6h. According to literature findings is nantokite formed through a reaction
between chloride and cuprous ions dissolved from cuprite [70, 73]. After 14 cycles were
the circular features no longer visible and local clustered features were randomly
observed, Fig.5.6d. Due to the volume expansion of the corrosion products, the focus
of the optical camera in the CRM was lifted with approximately 1µm to enable a sharp
image to be obtained, Fig. 5.6e. Generated CRM images provided evidence of cuprite
in the surrounding lower region (Fig.5.6i), while the corrosion products mostly
consisted of paratacamite in the upper region (Fig. 5.6j). The height difference
between nantokite and paratacamite further confirmed the concomitant volume
expansion within the patina during this transformation process, Figs.5.6d-j.
Both cuprite and nantokite were identified with CRM on bare Cu sheet, Cu15Zn
and Cu5Al5Zn surfaces pre-deposited with NaCl and exposed to wet/dry cycles. The
occurrence of nantokite was, in accordance with findings from the marine field
exposure, significantly more abundant on bare Cu sheet and Cu4Sn compared with
Cu15Zn and Cu5Al5Zn. Furthermore, no paratacamite was observed by means of
CRM on either Cu15Zn or Cu5Al5Zn, whereas this phase was readily detected on Cu
sheet and Cu4Sn after 14 cycles of exposure. When comparing all results was the
same patina reaction pathway evident in the laboratory exposures with humid air for
synthetically grown CuCl and surfaces pre-deposited with NaCl, and at marine field
conditions.

49
 
 Figure 5.6. Optical images ((a)-
(e)) and corresponding
combined Raman mapping
images (laser source of 532 nm,
(f)-(j)) obtained with CRM of the
Cu2O band (blue, integrated
between 150 and 250 cm-1),
CuCl band (red, integrated
between 250 and 350 cm-1) and
the OH band in Cu2(OH)3Cl
(green, integrated between 3300
and 3500 cm-1), of the patina
formed on Cu4Sn pre-deposited
with NaCl (4 μg/cm2) and
exposed for 1, 2, 6 and 14
wet/dry cycles at 90% RH. (e)
image obtained at the same area
as (d) but with the focus of the
optical camera lifted 1µm.
(Paper V)

50
5.3 The initial formation of Zn- and Zn/Al-hydroxycarbonates reduces the
sensitivity of Cu15Zn and Cu5Al5Zn to chloride-induced corrosion, and also
the release of zinc from Galfan at marine conditions. (Papers II, IV, V)

Complementary IRAS analyses were performed to examine corrosion product

formation on bare Cu sheet and the Cu-based alloy surfaces pre-deposited with NaCl
and exposed to wet/dry cycles. Comparative analyses were obtained via e.g. GDOES
for samples exposed to the marine outdoor test site. Improved surface properties
induced by the formation of hydroxycarbonates were further elucidated for both the
Cu-based alloys and for the Zn-Al alloys.
Figure 5.7 displays ex-situ IRAS spectra obtained after exposures to 14 wet/dry
cycles for bare Cu sheet, Cu4Sn, Cu15Zn and Cu5Al5Zn, respectively. Starting from
lower wavenumber and going upwards was the peak at 651 cm-1, attributed to the
vibration of Cu2O, cuprite [158], identified for all materials. A broad band ranging from
1300 to 1600 cm-1 with two resolved peaks located at 1395 and 1515 cm-1 was evident
in the spectra of Cu15Zn and Cu5Al5Zn, but barely observed for Cu sheet and Cu4Sn.
These bands are most likely assigned to anti-symmetric stretching modes of carbonate
(CO32-) [148], possibly in hydrozincite (Zn5(OH)6(CO3)2) and/or hydrotalcite
(Zn6Al2(OH)16CO3·4H2O). In the higher wavenumber range was a broad band
observed for both Cu15Zn and Cu5Al5Zn in the range between 3000 to 3700 cm-1, a
band that commonly is attributed to hydroxide ions (OH-) or water.

0.5 Cu2O
Absorbance (- log(R/R0))

- 2-
0.4 OH /H2O CO3

Cu4Sn
0.3

Cu
0.2

Cu15Zn
0.1

Cu5Al5Zn
0.0
4000 3500 3000 2500 2000 1500 1000 500
-1
Wavenumber (cm )

Figure 5.7. Ex-situ IRAS spectra obtained on bare Cu sheet, Cu4Sn, Cu15Zn and Cu5Al5Zn
pre-deposited with NaCl (4 μg /cm2) and exposed to 14 wet/dry cycles at 90% RH. (Paper V)

51
 
 Figure 5.8 illustrates the depth profiles of zinc with GDOES for both Cu15Zn and
Cu5Al5Zn after 1 year of marine exposure. The presence of zinc-rich corrosion
products was evident and predominantly enriched within the patina when compared
with the bulk content. These observations further supported the presence of
hydrozincite (Zn5(OH)6(CO3)2) and/or hydrotalcite (Zn6Al2(OH)16CO3·4H2O),
primarily formed within the patina on Cu15Zn and Cu5Al5Zn, respectively.

Figure 5.8. Enrichment of zinc in the patina compared with its bulk content in relation to
copper for Cu15Zn (a) and Cu5Al5Zn (b) after 1 year of unsheltered marine exposure, based
on GDOES measurements. (Paper IV)

The presence of hydrozincite is important for the barrier properties on bare zinc
sheet and galvanized steel in chloride-rich environments [159]. Literature findings
report accelerated atmospheric corrosion of zinc in marine environments during an
initial period of NaCl spreading, combined with a promoted formation of hydrozincite
in the secondary spread zone characterized by a more alkaline pH. Hydrozincite is
reported to protect the surface from further corrosion to a much larger extent
compared with other basic zinc compounds due to its resistance to chloride diffusion
and relatively high stability [160]. Dissociated protons or metal ions at the surface
contribute to a negative surface charge possessed by hydrozincite at pH lower than 7
[159]
. The negatively charged surface of hydrozincite is capable to repel chloride ions,
which may result in the prevention of chloride-induced atmospheric corrosion for such
surfaces [159]. These findings are in good agreement with the earlier conclusions of less
occurrence and formation of nantokite on CuZn15 and Cu5Al5Zn compared with bare
Cu sheet and Cu4Sn, providing an explanation for the different extent of corrosion
product flaking of the alloys investigated.

52
 Similar effects of hydrotalcite have been elucidated in the literature [65] with
improved barrier properties of corrosion products as observed on Zn-Al coatings
compared to bare Zn/galvanized steel in chloride-rich environments [161]. Zinc release
patterns induced by the interaction of humidity and rainwater on the surface during
long-term field exposures are given as an example. Regardless if zinc-rich phases
dominated the patina on both zinc and Galfan after longer exposure period, a
significantly lower (approximately twice as low) released amount of zinc was
observed from Galfan compared with bare zinc sheet throughout the 5-year exposure
period. Detailed corrosion product analysis revealed Zn5(OH)6(CO3)2 as one of the
main corrosion products formed on bare zinc sheet [147] and Zn6Al2(OH)16CO3·4H2O
on Galfan.

5.4 Similar corrosion products form on Galfan and bare Zn sheet and on
Galvalume and bare Al sheet, respectively, upon accelerated chloride test
conditions. (non-published data)

Accelerated N-VDA-tests were performed on bare Zn and Al sheet, Galfan and

Galvalume. Corrosion product formation was analyzed by means of SEM/EDS, IRAS
and GIXRD. The aim was to evaluate whether the accelerated corrosion test in a
realistic way could mimic the behavior (similar corrosion products and formation
mechanisms) of Zn-Al coatings on steel as in automotive environments of high
chloride content (or at chloride-rich marine conditions) [119].

Figure 5.9. SEM images of corrosion products formed at N-VDA test conditions on bare Zn
sheet exposed for 1 (a) and 7 (b) days, forming carbonate-rich corrosion products (c), and
on Galfan exposed for 1 (d) and 7 (e) days, forming chloride-rich corrosion products (f).

53
 
 The morphology of corrosion products formed on bare Zn sheet and Galfan during
the first week of the VDA test exposure is presented in Fig.5.9. Galfan revealed very
similar corrosion behavior as bare Zn sheet. Randomly distributed corrosion products
were present to a large extent on the surfaces already after 1 day of exposure. After 7
days were layer-structured patinas observed for both bare Zn sheet, Figs.5.10a-b and
Galfan, Figs.5.10d-e. ZnO, Zn(OH)2 and Zn5(OH)8Cl2·H2O were the main corrosion
products identified on both bare Zn sheet and Galfan with Al2O3,
Zn6Al2(OH)16CO3·4H2O and/or Zn2Al(OH)6Cl·2H2O additionally detected on Galfan
during the initial stages of the test. Sheet-like corrosion products were observed on
Galfan after 4 days of exposure, Fig.5.9f, and were predominantly composed of Cl,
Zn, Al and O, possibly assigned as Zn5(OH)8Cl2·H2O and/or Zn2Al(OH)6Cl·2H2O.
After longer exposure periods was Zn5(OH)6(CO3)2 the dominating constituent of the
patina, possibly present in the round-clustered features containing significant amounts
of Zn, C and O, demonstrated for bare Zn sheet exposed for 5 days, Fig.5.9c.

Figure 5.10. SEM images of corrosion products formed on bare Al sheet at N-VDA test
conditions exposed for 1 (a) and 7 (b) days, forming aluminum-rich corrosion products (c)
and Galvalume exposed for 1 (d) and 7 (e) days, with corrosion products forming locally
occurring platelets (f).

Galvalume revealed a similar corrosion behavior as bare Al sheet due to its high
alloy content of aluminum. Circular corrosion products were formed after 1 day of
exposure and were largely dependent on the NaCl interaction. These corrosion
products gradually covered the whole surface after 7 days of accelerated testing of
both bare Al sheet, Figs.5.10a-b, and of Galvalume, Figs.5.10d-e. Deposition of
chlorides highly influenced the corrosion of both Galvalume and Al due to the rapid

54
local damage of the compact native thin film of Al2O3. AlOOH and Al(OH)3 were
preferentially formed on bare Al sheet during initial stages of the accelerated testing,
and on Galvalume during intermediate stages. The bare Al surface revealed a fine-
grain surface patina when exposed for 4 days (Fig.5.10c) and micron-sized crystalline
corrosion products (Fig.5.10b), containing significant amount of Al and O. In addition,
Zn-Al containing corrosion products, Zn6Al2(OH)16CO3·4H2O and/or
Zn2Al(OH)6Cl·2H2O were identified on the Galvalume surface. Islands with platelet-
like morphologies were preferentially formed in zinc-rich interdendritic regions after
5 days of exposure, Fig.5.10f. SEM observations, and proposals in the scientific
literature [68], suggest these corrosion products to consist of Zn6Al2(OH)16CO3·4H2O.
This could not be verified in this study.
A comparison of the corrosion behavior of bare metals (Zn and Al) and alloys
(Galfan and Galvalume) is schematically given in Fig.5.11. Galfan revealed a similar
corrosion behavior as bare Zn sheet, whereas Galvalume exhibited similar behavior
as bare Al sheet.

Figure 5.11. Comparison of the corrosion behavior of bare Zn and Al sheet and the Zn-Al
alloys (Galfan and Galvalume) after exposure to accelerated N-VDA test conditions.

55
 
5.5 Laboratory set-ups with exposures to chloride-rich environments were
able to successfully reproduce the predominating corrosion products formed
at marine outdoor conditions for the Zn-Al coatings, bare Cu sheet and the
Cu-based alloys. (Papers I, II, IV, V)

5.5.1 Zn-Al alloy coatings

To obtain a comprehensive understanding of corrosion product formation and their
evolution for Zn-Al alloys exposed to chloride-rich environments, are all corrosion
products identified on Galfan and Galvalume upon laboratory, unsheltered marine
field and accelerated exposures compiled and displayed in Table. 5.1 based on the
multi-analytical approach employed in this thesis.
The relatively simple laboratory exposures with pre-deposited NaCl and humidity
or chloride-containing media were able to generate the same predominating corrosion
products formed of Galfan and Galvalume after long-term marine field exposures,
even though in different amounts and relative proportions. The only exception was
the lack of formation of NaZn4Cl(OH)6SO4·6H2O, present after long-term marine field
exposure conditions. This was primarily attributed to the lack of SO2 or sulfate
deposition involved in the laboratory wet/dry cyclic set-ups and accelerated test.

Table 5.1. Compilation of corrosion products identified on Galfan and Galvalume after
laboratory-, marine field- and accelerated exposures for different time periods. (GF-Galfan,
GV-Galvalume, *- tentative phases)

Laboratory Field exposure Accelerated exposure

Corrosion product
exposure (Marine site) (N-VDA-test)
ZnO GF GV GF GV GF GV
Zn(OH)2 GF* GV* GF* GV* GF GV*
Zn5(OH)6(CO3)2 GF GV*
Zn5(OH)8Cl2·H2O GF GV* GF GV* GF GV
NaZn4Cl(OH)6SO4·6H2O GV* GF GV*
Al2O3 GF GV GF GV GF GV
AlOOH GV* GV
Al(OH)3 GF* GV* GF* GV GF* GV
ZnAl2O4 GF* GF* GF*
Zn6Al2 (OH)16CO3·4H2O GF* GV* GF GV* GF GV
Zn2Al(OH)6Cl·H2O GF* GV* GF* GV* GF* GV*

56
  

5.5.2 Cu and Cu-based alloys

A compilation of corrosion products identified within the patina of Cu sheet and
the Cu-based alloys exposed to chloride-rich laboratory conditions via wet/dry cyclic
sequences and outdoor marine conditions is given in Table 5.2 based on the
multianalytical investigation presented earlier.
Exposures in the relatively simple laboratory set-ups with pre-deposited NaCl and
humidified air were able to successfully reproduce the same predominating corrosion
products, although in different relative proportions and surface coverage, formed
during long-term outdoor marine conditions.
Table 5.2. Compilation of corrosion products identified on bare Cu sheet and Cu-based
alloys exposed to chloride-rich laboratory and marine field exposures. (*- tentative phases)

Corrosion products Laboratory exposure Field exposure (marine site)

Cu2O Cu Cu4Sn Cu15Zn Cu5Al5Zn Cu Cu4Sn Cu15Zn Cu5Al5Zn

CuCl Cu Cu4Sn Cu15Zn Cu5Al5Zn* Cu Cu4Sn Cu15Zn Cu5Al5Zn*
Cu2(OH)3Cl Cu Cu4Sn Cu Cu4Sn Cu15Zn Cu5Al5Zn
SnO2 Cu4Sn
ZnO Cu15Zn* Cu15Zn
Zn(OH)2 Cu15Zn Cu15Zn*
Zn5(OH)6(CO3)2 Cu15Zn* Cu15Zn*
Zn5(OH)8Cl2·H2O Cu15Zn* Cu15Zn* Cu5Al5Zn*
Al2O3 Cu5Al5Zn* Cu5Al5Zn
Zn6Al2 (OH)16CO3·4H2O Cu5Al5Zn* Cu5Al5Zn
Zn2Al(OH)6Cl·H2O Cu5Al5Zn* Cu5Al5Zn*

5.6 General scenarios for patina evolution established for Zn-Al coatings
and corrosion product flaking mechanisms proposed for Cu-based alloys in
chloride-rich atmospheric environments. (Papers II, V)

5.6.1 Zn-Al alloy coatings

Previous investigations have established general sequences for the evolution of the
most commonly occurring corrosion products on bare Zn sheet [53] and pure Al sheet
[60, 162]
at different atmospheric conditions.

57
 
 The established evolution scenarios of relevance for chloride-rich conditions
(sheltered conditions) are presented in Fig.5.12 and compared with findings and
proposed scenarios from this study for the investigated Zn-Al alloy coatings
(unsheltered conditions) [14].
In moist atmospheres are zinc- and aluminum oxides and/or hydroxides formed
immediately on all materials. Atmospheric CO2 dissolves in the aqueous adlayer and
reacts with hydroxides, rapidly forming hydrozincite (Zn5(OH)6(CO3)2) and
hydrotalcite (Zn6Al2(OH)16CO3·4H2O). Triggered by chlorides, hydroxychlorides,
simonkolleite (Zn5(OH)8Cl2·H2O) is subsequently formed on bare Zn sheet, and
Zn2Al(OH)6Cl·2H2O and/or Zn5(OH)8Cl2·H2O on the Zn-Al alloy coatings. The
evolution from one phase to another can in addition to chemical transformations
proceed via previously proposed ion-exchange mechanisms [53], since all
hydroxycarbonates and hydroxychlorides (and hydroxysulfates) possess structural
resemblance and layered structures held together by different anions such as carbonate,
chloride and/or sulfate.

Figure 5.12. Established sequences of corrosion product formation on bare zinc

sheet/galvanized steel (left) and bare Al sheet (right) in chloride-rich atmospheric
environments compared with the proposed sequence for Al-Zn-coatings of Galfan and
Galvalume (middle) based on findings in this study. Vertical arrows indicate the evolution of
one phase into the next phase and phases without vertical arrow can exist simultaneously
next to each other. Underlined phases are also observed in corresponding sequences for bare
Zn and bare Al. (Paper II)

Marine environments are not only characterized by abundant chloride deposition,

but also by sulphate deposition, e.g. from sea spray and gaseous SO2 [144].
Consequently, NaZn4Cl(OH)6SO4·6H2O, another phase with a layered structure, has
been identified after long-term exposure perods on both bare Zn [144] and Galfan [143].
The predominating corrosion product formed on bare Al sheet is Al(OH)3, a

58
predominating phase also on Galvalume after long-term exposures in marine
environments [14]. Besides being of importance from a more fundamental atmospheric
corrosion mechanistic perspective is the proposed evolution sequence for Al-Zn
coatings important for elucidating long-term barrier properties and corrosion
characteristics of these and similar alloys in chloride-rich environments.
5.6.2 Cu and Cu-based alloys
Bare Cu sheet and Cu-based alloys were investigated in chloride-rich environment
with the goal of revealing the possible mechanism behind corrosion product flaking.
The established patina evolution scenario on bare Cu sheet [70] was shown to be valid
also for the Cu-based alloys upon exposures in chloride-rich conditions, both at
laboratory and field conditions. In addition, other phases were formed and identified
related to reactions between the main alloying elements (Sn, Zn and Al) and given
atmospheric constituents. These corrosion products turned out to be essential for the
extent of corrosion product flaking for the different materials investigated at chloride-
rich conditions.
A summary of all findings are schematically displayed in Fig.5.13, showing the
sequence of corrosion products formed on bare Cu sheet and the Cu-based alloys in
chloride-rich environments. Cuprite (Cu2O) forms rapidly on all materials at humid
conditions, while zinc oxide (ZnO) and/or aluminum oxide (Al2O3) form on Cu15Zn
and Cu5Al5Zn. Hydroxides react with dissolved atmospheric CO2 and form
hydrozincite (Zn5(OH)6(CO3)2) and/or hydrotalcite (Zn6Al2(OH)16CO3·4H2O) on
Cu15Zn and Cu5Al5Zn, respectively. High deposition rates of chloride result in the
local formation of nantokite (CuCl) through reactions between chloride ions and
dissolved cuprous ions. This phase was in these studies significantly more abundant
on bare Cu sheet and Cu4Sn compared with Cu15Zn and Cu5Al5Zn. As a
consequence revealed the former materials a significantly higher sensitivity to
chloride-induced corrosion compared with the latter materials. Nantokite easily
transforms to e.g. paratacamite (Cu2(OH)3Cl) through reactions with water and
oxygen. Paratacamite is a more voluminous phase, with a molar volume (molar mass
divided by the density) of 61.0 cm3 mole-1 compared with nantokite, of 23.9 cm3 mole-
1
. The transformation process of nantokite to paratacamite hence contributes to a
significant volume expansion. The discontinuous presence of nantokite within the
patina and its continuous formation and transformation to paratacamite induce internal
physical stresses, which result in a separation between the inner patina layer (mainly
cuprite) and the outer patina layer (mainly paratacamite), causing corrosion product
flaking primarily observed on bare Cu sheet and Cu4Sn.

59
 
Figure 5.13. Sequence of corrosion products formed on bare Cu sheet, Cu4Sn, Cu15Zn and
Cu5Al5Zn upon long-term unsheltered exposures in a marine environment, and during short-
term laboratory exposures in chloride-containing humid environments. Key processes
governing the mechanism of flaking are indicated in blue. (Paper V)

Minor occurrence and lack of corrosion product flaking for Cu15Zn and Cu5Al5Zn,
respectively, were attributed the formation and presence of hydroxycarbonates
(hydrozincite and/or hydrotalcite) within the patina that altered the surface chemistry
and surface charge in chloride-rich environment. As a consequence the formation of
nantokite and subsequent transformation to paratacamite were suppressed for these
alloys.

60
6 Summary and outlook

The main objective of this doctoral thesis work has been to provide a fundamental
understanding of the link between microstructure and corrosion initiation and
corrosion product evolution and sequences for Zn-Al coatings on steel and of Cu-
based alloys in chloride-rich atmospheric conditions via short-term laboratory and
long-term outdoor marine environments, summarized in Fig.6.1. The investigated
alloys are all commercially available and used in different automotive applications
(Galfan (Zn5Al) and Galvalume (Zn55Al)) and for outdoor building applications
(Zn55Al, Cu4Sn, Cu15Zn, Cu40Zn and Cu5Zn5Al). A multianalytical approach has
been employed using a combination of surface sensitive in-situ and ex-situ analytical
techniques to investigate microstructural characteristics and corrosion product
initiation, formation, evolution and surface distribution. The influence of surface
heterogeneity on corrosion initiation was explored based on microgalvanic effects and
corrosion product evolution elucidated via short-term laboratory and long-term field
exposures. Main conclusions are summarized below with an outlook for possible
further investigations.
An obvious influence of the microstructure on corrosion initiation has been
observed for Galfan and Galvalume upon laboratory and field exposures in chloride-
rich environments. Initial corrosion was triggered by microgalvanic effects between
active zinc-rich phases and passive aluminum-rich phases where local corrosion cells
were created. Based on cyclic laboratory exposures of Galfan pre-deposited with NaCl
in humidified air it was apparent that corrosion product initiation predominantly takes
place in the zinc-richer microstructural phase adjacent to the aluminum-richer phase.
These corrosion products extend with time following the direction of lamellas or rods,
and form local clusters covering the surface.
High-temperature formed Al2O3 is the predominant surface oxide of Galvalume
prior to exposure, an oxide being subject to local destruction upon interaction with
chloride ions. Corrosion initiation and propagation of zinc-rich corrosion products
primarily take place in interdendritic zinc-rich microstructural phases. With time also
aluminum-rich corrosion products form and evolve and dominate the entire surface
after long-term exposure periods in chloride-rich environments. Zinc is preferentially
released from the surface compared with aluminum from Galvalume, both during the
immersion test and the flow cell test at open circuit potential conditions, and upon the
long-term unsheltered marine field exposure.

61
 
Figure 6.1. Compilation of main research findings of this doctoral thesis.

An evident microstructural influence on the initial formation of corrosion products

has been observed for the Cu40Zn alloy upon laboratory exposures with humidified
air and low amounts of pre-deposited NaCl. Cu2O and ZnO preferentially form in the
slightly zinc-richer β-phase crystals adjacent to the α-phase matrix. A microgalvanic
cell forms for each Cu island and its surrounding Zn matrix on the Cu-Zn patterned
sample. This leads to the separation of Cu acting as the cathode and Zn as the anode
beneath the NaCl droplet. Local formation of Cu2O, ZnO and CuCl were identified
respectively on the Cu island, Zn matrix and the boundary in-between, whereas
circularly distributed Zn5(OH)6(CO3)2, predominantly forms in the secondary
spreading areas and clusters of Zn5(OH)8Cl2·H2O form outside these circles.
The laboratory set-up with humidified air and NaCl was able to reproduce the same
corrosion products on both investigated alloy groups, although in different proportion
and surface coverage, as identified at unsheltered outdoor marine conditions. Main
corrosion products formed on Galfan and Galvalume, during atmospheric exposure in
the chloride-rich laboratory and marine environments include the initial formation of
ZnO, Al2O3 and/or ZnAl2O4 and subsequent formation of Zn6Al2(OH)16CO3·4H2O,

62
and Zn2Al(OH)6Cl·2H2O and/or Zn5(OH)8Cl2·H2O. Corrosion products identified
within the patina on bare Cu sheet and commercial Cu-based alloys exposed at similar
chloride-rich conditions include an outer layer of Cu2(OH)3Cl and an inner layer of
Cu2O, separated by an discontinuous layer of CuCl. Additional minor patina
constituents include SnO2 (Cu4Sn), Zn5(OH)6(CO3)2 and Zn5(OH)8Cl2·H2O (Cu15Zn
and Cu40Zn), Zn6Al2(OH)16CO3·4H2O/ Zn2Al(OH)6Cl·2H2O/Zn5(OH)8Cl2·H2O and
Al2O3 (Cu5Al5Zn).
The marine exposure resulted in a patina of poorly adherent corrosion products on
bare Cu sheet and Cu4Sn that easily flaked from the surface, more adherent corrosion
products with less or non-significant extent of flaking were formed on Cu15Zn and
Cu5Al5Zn, respectively. The tendency for flaking of corrosion products was
significantly connected to the occurrence of CuCl, and attributed to a volume
expansion and internal stresses within the patina induced by the gradual
transformation of CuCl to Cu2(OH)3Cl. The fact that the Cu15Zn and Cu5Al5Zn
alloys were significantly less sensitivity to chloride-induced corrosion product flaking
compared with bare Cu sheet and Cu4Sn can be explained by a reduced interaction of
chlorides with the former two alloys due to the initial formation and presence of Zn-
and Zn/Al-hydroxycarbonates that hinder chloride surface interactions.
General scenarios for corrosion product evolution on Zn-Al coatings and the
corrosion product flaking mechanism on Cu sheet and Cu-based alloys in chloride-
rich environments are proposed based on findings from both laboratory and field
exposures. The findings are of importance for the understanding of corrosion-related
properties of these materials. Zn- and Zn/Al-hydroxycarbonates, Zn5(OH)6(CO3)2 and
Zn6Al2(OH)16CO3·4H2O were two very important corrosion products identified on the
Zn-Al and the Cu-based alloys. Their presence reduces, or hinders, the formation of
CuCl, and hence chloride-induced corrosion product flaking for the Cu15Zn and
Cu5Al5Zn alloys, and reduce the long-term annual release of zinc from Galfan
compared with bare zinc sheet at marine conditions.
This thesis work provides novel in-depth understanding of corrosion initiation and
corrosion product evolution at atmospheric conditions for Zn-Al coatings on steel and
for Cu-based alloys in chloride-rich environments. However, there are still aspects of
large importance for such environments that require further investigations. Even
though chlorides are the main corrosion stimulators at marine conditions are effects
of other pollutants such as aerosol particles, SO2/SO42-, NO2 and O3 on corrosion
initiation and corrosion product formation and evolution important to investigate at
atmospheric conditions. Acidified marine aerosols are believed to be of increasing
importance for the atmospheric corrosion of metals [160]. Such effects could be further
investigated via systematic laboratory exposures and evaluated using e.g. in-situ

63
 
IRAS. Moreover, due to the heterogeneous distribution of pre-deposited NaCl on the
surface, local corrosion was largely triggered and the effect of the microstructure and
microgalvanic cells on corrosion initiation difficult to assess. Future studies could be
facilitated by using highly diluted NaCl solutions.
The multi-analytical approach employed in this doctoral thesis provides a generic
tool box that is applicable for detailed studies to assess the relation between corrosion
initiation and complex microstructures of any alloy systems, e.g. Zn-Al-Mg alloy
coatings on steel.

64
Acknowledgements

The work presented within this thesis would not be possible without the help and
support from many people. I would like to express my sincere gratitude to those have
made contributions to my doctoral studies during the past four years:
Prof. Inger Odnevall Wallinder, my main supervisor; I really appreciate your
professional supervision on me with immense supporting, endless patient and
continuous encouragement. Your extensive knowledge and brilliant suggestions
always guide me to the right direction for my graduate study. Special thanks for the
extraordinary efforts on finalizing my thesis.
Prof. Christofer Leygraf, my co-supervisor; thank you so much for providing the
opportunity for me to join this great group. Your creative ideas and scientific
comments are of great significance for the progress during my doctoral study and also
the discussion with you, no matter on science or life, always inspire and encourage
me and help me grow up.
Prof. An Lin, Prof. Dihua Wang and Prof. Fuxing Gan, my former supervisors in
Wuhan University, China; I am sincerely grateful for supporting and helping me to
study abroad. Special thanks to Prof. An Lin for immense help on my future career.
Prof. Jiazhu Li; many thanks for introducing me to Christofer and helping me to
get this precious chance to start a new journey.
Prof. Jinshan Pan; thank you a lot for not only sharing your professional
knowledge in science but also encouragement in life.
Ping Qiu and Klara Midander; great thanks for guiding me into my doctoral study
and teaching me the basic knowledge and the operation of several techniques, which
makes my first year here much easier.
Prof. Kevin Ogle, Prof. Polina Volovitch and Thanh-Nam Vu at Ecole Nationale
Supérieure de Chimie de Paris, France, my co-authors in the first paper; thanks for the
scientific input of AESEC measurements and invaluable discussions.
Sara Goidanich at Politecnico di Milano, Italy and Gunilla Herting, my co-authors
in the copper paper; thanks for your important contribution. Special thanks to Gunilla
Herting for AAS training and great helping with different issues.
Rodrigo Robinson and Birgit Brandner at SP Technical Research Institute, Sweden
for ESEM and CRM training and also informative discussions.

65
 
 Fan Zhang, Mattias Forslund, Eleonora Bettini and Majid Sababi for invaluable
help with SKPFM measurements and suggestions.
Oscar Karlsson, Niklas Pettersson and Mats Randelius at Swerea KIMAB, Sweden
for effort on FEG-SEM, FIB-SEM and GDOES measurements.
Gerald Luckeneder at VoestAlpine, Austria for helping with the N-VDA test.
Neda Mazinanian, Tao Jiang and Xin Wang for kindly helping with the roof work.
Xiaoyan Liu, Olga Krivosheeva, Jonathan Liljeblad and Zahra Besharat, my
present and former room-mates; thank you for sharing an office with me.
All the present and past colleagues in the Div. Surface and Corrosion Science;
many thanks for creating the friendly working atmosphere and helping with different
matters.
All my Chinese friends in Stockholm, especially those living in Kungshamra; great
thanks for creating an enjoyable environment and relax times. Life would be boring
without you.
CSC, the China Scholarship Council, RFCS, European Union’s Research Fund for
Coal and Steel research programme, and ECI, the European Copper Institute are
gratefully acknowledged for financial support.
My big family, both in Zhang and Yang; thank you so much for your endless
understanding and support.
Miao Yang, my husband; I couldn’t be happier with your presence in my life. Your
love, consideration and unlimited support mean the world to me.
I would like to express my sincere appreciation to my father, Bingshu Zhang, and
my mother, Libai Xiong (1956-2006), for loving and supporting me in all situations
throughout all years as well as guiding me to become a strong and independent person.

 
 
 
 
 
 
 

66
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