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in materials research
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advances in materials research
7
advances in materials research
SeriesEditor-in-Chief: Y.Kawazoe
SeriesEditors: M.Hasegawa A.Inoue N.Kobayashi T.Sakurai L.Wille
The series Advances in Materials Research reports in a systematic and comprehensive
wayonthelatestprogressinbasicmaterialssciences.Itcontainsboththeoreticallyand
experimentallyorientedtextswrittenbyleadingexpertsinthefield.AdvancesinMaterials
ResearchisacontinuationoftheseriesResearchInstituteofTohokuUniversity(RITU).
1 MesoscopicDynamicsofFracture
ComputationalMaterialsDesign
Editors:H.Kitagawa,T.Aihara,Jr.,andY.Kawazoe
2 AdvancesinScanningProbeMicroscopy
Editors:T.SakuraiandY.Watanabe
3 AmorphousandNanocrystallineMaterials
Preparation,Properties,andApplications
Editors:A.InoueandK.Hashimoto
4 MaterialsScienceinStaticHighMagneticFields
Editors:K.WatanabeandM.Motokawa
5 StructureandPropertiesofAperiodicMaterials
Editors:Y.KawazoeandY.Waseda
6 FiberCrystalGrowthfromtheMelt
Editors:T.Fukuda,P.Rudolph,andS.Uda
7 CharacterizationofCorrosionProducts on SteelSurfaces
Editors:Y.WasedaandS.Suzuki
Y. Waseda S. Suzuki (Eds.)
Characterization
of Corrosion Products
on Steel Surfaces
With205Figures, 2 in color and 16 Tables
123
ProfessorYoshioWaseda
ProfessorShigeruSuzuki
InstituteofMultidisciplinary
ResearchforAdvancedMaterials
TohokuUniversity
2-1-1Katahira,Aoba-ku
Sendai980-8577,Japan
E-Mail:[email protected],[email protected]
SeriesEditor-in-Chief:
ProfessorYoshiyukiKawazoe
InstituteforMaterialsResearch,TohokuUniversity
2-1-1Katahira,Aoba-ku,Sendai980-8577,Japan
SeriesEditors:
ProfessorMasayukiHasegawa
ProfessorAkihisaInoue
ProfessorNorioKobayashi
ProfessorToshioSakurai
InstituteforMaterialsResearch,TohokuUniversity
2-1-1Katahira,Aoba-ku,Sendai980-8577,Japan
ProfessorLucWille
DepartmentofPhysics,FloridaAtlanticUniversity
777GladesRoad,BocaRaton,FL33431,USA
ISSN1435-1889
ISBN-103-540-35177-9SpringerBerlinHeidelbergNewYork
ISBN-13978-3-540-35177-1SpringerBerlinHeidelbergNewYork
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Preface of Series by the Editor-in-Chief
Thisbookentitled“CharacterizationofCorrosionProductsonSteelSurfaces”
is published as the seventh volume in the series of “Advances in Materials
Research”editedbyProfessorsYoshioWasedaandShigeruSuzuki.Thebook
is composed of twelve chapters, the contents of which together try both to
solve the currently important basic problems in corrosion and to contribute
tothesteelmakingindustriesintherealizationofsubstantiallybetterprocess
engineering. It will contribute to society worldwide “for preventing environ-
mental degradation” which the editors stressed as the subtitle of the book.
The book contains recent high level research results starting from the funda-
mental mechanism of corrosion to various measurement tools which are used
for characterization to reveal the structures of corrosion products both sta-
tically and dynamically. As series editor, I would like to thank Dr. Claus
AschelonofSpringer-Verlag,whohasalwayshadinterestinandkindlytaken
careofourresearchactivitybyencouragingpublicationinthisseriesofbooks.
Sendai, December 2005 Yoshiyuki Kawazoe
Preface
The structure of corrosion products, also referred to as rust, formed on the
steelsurfaceisofgreatinterest,becausethecorrosionrateofsteelisknownto
dependstronglyontheconditionofsuchcorrosionproductscoveringthesur-
faceasaprotectivefilm.Forexample,thecorrosionrateofweatheringsteelin
the atmosphere is found to be considerably suppressed when an amorphous-
like rust layer is formed. This enables us to reduce maintenance costs and
also contributes to the beneficial utilization of iron natural resources.
Ontheotherhand,corrosionproductsofironandsteelareformedbyre-
action of iron and its alloying elements with reactive species, such as oxygen
and water, which originate from the atmosphere. Corrosion products are fre-
quentlynotdescribablebythetypicalstructureofironoxides.Thisindicates
thatthestructureofcorrosionproductsisconsideredtobeverycomplicated,
and some parts of such iron oxides are assigned to the amorphous state for
this reason. Thus, a method for characterizing the atomic-scale structure of
corrosion products is strongly required, because it is likely to be related to
a corrosion mechanism of metallic materials. Lifetime of steel is sometimes
dominated by environmental degradation, so that the structure of corrosion
productsformedonthesurfaceofsteelduringexposuretoairforaprolonged
period is of great importance. For example, the Delhi iron pillar, which was
made in India about 1600 years ago, still stands without serious degrada-
tion, whereas steel structures produced by modern manufacturing methods
are sometimes replaced after use for a few tens years.
Analytical techniques, such as X-ray diffraction, Fourier-transform in-
frared spectroscopy, electron probe microanalysis and Mo¨ssbauer spectro-
scopy, have been used for obtaining the structure and chemical composition
of corrosion products formed on the surface of iron and steel under various
atmospheric conditions. By applying these methods, for example, the cor-
rosion product formed on the surface of the ancient Delhi iron pillar has
been found to consist of α-FeOOH, γ-FeOOH, δ-FeOOH, Fe O and iron
3 4
hydrogen phosphate hydrates. Mo¨ssbauer spectroscopy also provides super-
paramagnetism data on oxyhydroxides, being types of FeOOH, suggesting
that particles of these oxyhydroxides in corrosion products are very fine. Re-
sults from the extended X-ray absorption fine structure (EXAFS) method
indicate that the fundamental local ordering structure of corrosion products
VIII Preface
isrepresentedmainlybyFeO octahedralunitsandhydrogenatomsarequite
6
likely to be intercalated in these structural units of ferric oxyhydroxides. By
applying these methods, characterization including structure of rust formed
on the surface of weathering steel has been carried out, in order to make
clear the corrosion protective property of this particular steel. Nevertheless,
our present understanding of the atomic-scale structure of rust is far from
complete for several reasons; the component phases in rust formed on the
surface of weathering steel show imperfection of their structures and their
realistic structures of components appear to deviate from an ideal crystal-
lographic structure of typical iron oxides such as α-FeOOH and γ-FeOOH.
The structure of a very thin passive film formed on the stainless steel, which
plays an important role in its corrosion resistance, may be similar to that of
such oxides to some extent. Although the structure of the passive film is still
controversial, optical or semiconductor properties of the passive film have
been extensively studied coupled with electrochemical properties.
This book provides a critical, up-to-date evaluation starting with an ex-
tended introductory treatise on the fundamentals, followed by a description
of relatively new results, several advanced methods and techniques for mate-
rials characterization of corrosion products formed on the steel surface and
ends with their characterization. New information is given with respect to
corrosion products formed on the surface of iron-based alloys, containing
chromium,nickelorcopper,andweatheringsteelinsaltwater,becauseafew
percentofthesealloyingelementsareknowntobeaddedtoiron-basedalloys
inordertoimprovecorrosionprotectionofsteel.Ithasalsobeenthefocusing
point of this book to reveal the network structure consisting of FeO octahe-
6
dral units and its distortion from the ideal iron oxide case such as α-FeOOH
and γ-FeOOH. This includes how the alloying elements affect the structure
of rust formed on the surface of various iron-based alloys and steel.
The subject is approached from both the basic science and the applied
engineeringpointsofview.Themanyreferences,illustrationsandtablespro-
vide adequate help and guidance for specialists and non-specialists who wish
to become acquainted with the processing, controlling and characterization
of corrosion products formed on the steel surface.
Sendai Yoshio Waseda
December 2005 Shigeru Suzuki
Contents
1 CorrosionProtectionFunctionandBreakdownMechanism
of Passive Films on Stainless Steels
Katsuhisa Sugimoto ............................................. 1
1.1 Introduction ............................................... 1
1.2 Origin of Pit Initiation ...................................... 2
1.3 Suppression Mechanism of Passive Film Breakdown
by Alloyed Cr.............................................. 2
1.4 Composition of Passive Films Formed in Acid Chloride
Solutions .................................................. 3
1.5 Fabrication of Artificial Passivation Films ..................... 4
1.6 Evaluation of Corrosion Resistance of Artificial
Passivation Films........................................... 6
1.7 Dissolution Behavior of Fe O -Cr O Films.................... 7
2 3 2 3
1.8 Anodic Polarization Behavior of Fe-Cr Alloys .................. 8
1.9 Composition of Passive Films on Fe-Cr Alloys.................. 9
1.10 ComparisonofDissolutionBehaviorBetweenFe O -Cr O Artificial
2 3 2 3
Passivation Film and Real Passive Film on Fe-Cr Alloy.......... 10
1.11 Induction Period of Pitting on Fe-Cr Alloys.................... 11
1.12 Pitting Potentials of Fe-Cr Alloys in 1M HCl .................. 13
1.13 Dissolution of Locally Heterogeneous Fe O -Cr O Film......... 13
2 3 2 3
1.14 Mechanism of pit Initiation on Fe-Cr Alloy .................... 14
1.15 Summary.................................................. 16
References ..................................................... 16
2 Passivation Oxide Films and Rust Layers on Iron
Toshiaki Ohtsuka ............................................... 19
2.1 Introduction ............................................... 19
2.2 Passivation Oxide Films on Iron.............................. 19
2.3 Rust Formation on Iron and Steels ........................... 26
2.4 Potential Distribution and Ionic Transport..................... 28
2.5 Summary.................................................. 30
References ..................................................... 31
X Contents
3 Semiconductor Property of Passive Films and Corrosion
Behavior of Fe-Cr Alloys
Shinji Fujimoto, Hiroaki Tsuchiya................................. 33
3.1 Introduction ............................................... 33
3.2 The Photoelectrochemical Response .......................... 33
3.2.1 A Brief History of Photoresponse in Electrochemistry .... 33
3.2.2 Measurement of Photocurrent and Spectrum Separation .. 34
3.3 Passive Films on Cr and Fe-Cr Alloys in Sulphuric Acid......... 36
3.3.1 Photocurrent........................................ 36
3.3.2 Capacitance......................................... 38
3.3.3 Electronic Structure of Passive Films on Cr
and Fe-Cr Alloys formed in Acid Solution............... 39
3.4 Passive Film on Fe-18Cr Alloy formed
in Borate Buffer Solution.................................... 42
3.4.1 Photocurrent and Capacitance ........................ 42
3.4.2 Electronic Structure of Passive Films on Fe-18Cr Alloy
formed in Borate Buffer Solution ...................... 44
3.5 Correlation between Electronic Structure of Passive Films and
Corrosion Behaviour for Fe-Cr Alloys ......................... 45
3.6 Summary.................................................. 47
References ..................................................... 47
4 Mechanistic Study on Formation of Iron Hydroxides and
Oxides with FT-IR and UV Photospectroscopy
Atsushi Muramatsu, Kiyoshi Kanie................................ 51
4.1 Introduction ............................................... 51
4.2 Utilization of UV-vis and FT-IR ............................. 51
4.3 Precipitation from Aqueous Solutions ......................... 54
4.4 Simplest Complex of Iron.................................... 56
4.5 Change in Ferric Complexes with pH ......................... 58
4.6 UV Spectroscopy for the Direct Identification of Ferric Complexes 59
4.7 IR Spectroscopy for the Formation Mechanism of Particles....... 65
4.8 Characterization of Iron Oxides by FT-IR ..................... 69
References ..................................................... 74
5 StructuralCharacterizationforaComplexSystembyObtaining
Middle-Range Ordering
Yoshio Waseda, Shigeru Suzuki, Masatoshi Saito .................... 77
5.1 Introduction ............................................... 77
5.2 Theoretical Background and Methods......................... 78
5.3 Selected Examples of Middle-range Ordering Obtained by the
AXS Method Coupled with the RMC Simulation Technique...... 83
5.3.1 GeO Glass ......................................... 83
2
5.3.2 Amorphous ZrO Prepared by Hydrolytic Condensation .. 88
2
