Characterization of Corrosion Products on Steel Surfaces

Mục Lục

 

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 Fe2O3-Cr2O3 Films . . . . . . . . . . . . . . . . . . . . 7
1.8 Anodic Polarization Behavior of Fe-Cr Alloys . . . . . . . . . . . . . . . . . . 8
1.9 Composition of Passive Films on Fe-Cr Alloys . . . . . . . . . . . . . . . . . . 9
1.10 Comparison of Dissolution Behavior Between Fe2O3-Cr2O3 Artificial
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 Fe2O3-Cr2O3 Film. . . . . . . . . 13
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 Structural Characterization for a Complex System by Obtaining
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 GeO2 Glass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
5.3.2 Amorphous ZrO2 Prepared by Hydrolytic Condensation . . 88

Contents XI
5.3.3 Corrosion Products formed on the Steel Surface . . . . . . . . . 93
5.4 Summary. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
6 Corrosion Mechanism of Iron from an X-ray Structural
Viewpoint
Eiichiro Matsubara, Shigeru Suzuki, Yoshio Waseda …………….. 105
6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
6.2 Structure and Formation of Various Components of Corrosion
Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
6.3 Methods for In-situ and Ex-situ X-ray Diffraction . . . . . . . . . . . . . . 109
6.3.1 Sample Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
6.3.2 Diffraction Measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
6.4 X-ray Diffraction of Corrosion Products Formed Under Various
Conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
6.4.1 In-situ X-ray Diffraction of Corrosion Products Formed
During One-cycle Exposure to Wet
and Dry Atmospheres . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
6.4.2 In-situ XRD Diffraction of Corrosion Products Formed
During Multi-cycle Exposure to Wet
and Dry Atmospheres . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
6.4.3 Ex-situ XRD Diffraction of Corrosion Products
Extracted from Different Layers . . . . . . . . . . . . . . . . . . . . . . . 119
6.5 Formation Conditions of Different Components of Corrosion
Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
6.6 Summary. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
7 Surface Analysis of Oxides and Corrosion Products Formed
on Surfaces of Iron-based Alloys
Shigeru Suzuki …………………………………………. 131
7.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
7.2 Surface Analytical Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
7.3 Characterization of Thermally Oxidized
Surface Layers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
7.3.1 Oxidation of a Compositionally Modified Surface Layer . . . 136
7.3.2 Selective Oxidation of Less-noble Elements in Surface
Layers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
7.4 Iron Oxides Formed Under Atmospheric Corrosion. . . . . . . . . . . . . . 146
7.4.1 Fine Corrosion Products Formed on a Native Oxide
Layer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
7.4.2 Sources of Corrosion Products Formed on Iron Surfaces. . . 151
7.5 Summary. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156

XII Contents
8 Characterization of Rust Layers on a Plain-Carbon Steel and
Weathering Steels Exposed to Industrial and Coastal Atmosphere
for Years
Katsuhiko Asami ……………………………………….. 159
8.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
8.2 Experimental Procedures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
8.2.1 Compositions of Steel Specimens. . . . . . . . . . . . . . . . . . . . . . . 161
8.2.2 Exposure Conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
8.2.3 Specimen Preparation for Characterization . . . . . . . . . . . . . . 163
8.2.4 Characterization Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
8.3 Results. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
8.3.1 SEM Observation of Cross-Sections of Rust Layers . . . . . . . 167
8.3.2 XRD Analysis of Rust Surface. . . . . . . . . . . . . . . . . . . . . . . . . 168
8.3.3 EPMA Analysis of Rust Surface . . . . . . . . . . . . . . . . . . . . . . . 170
8.3.4 EPMA Analysis of Cross-Section of Rust Layers . . . . . . . . . 171
8.3.5 TEM/ED Analysis of Cross-Section of Rust Layers. . . . . . . 177
8.3.6 In-depth Distribution of Rust Components . . . . . . . . . . . . . . 180
8.3.7 Abundance of Rust Components . . . . . . . . . . . . . . . . . . . . . . . 183
8.4 Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 188
8.4.1 Effect of Amorphous Rust Layer . . . . . . . . . . . . . . . . . . . . . . . 189
8.4.2 Effects of Akagan ́eite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 192
8.4.3 Correlation between Akagan ́eite and Magnetite . . . . . . . . . . 193
8.4.4 Effect of Lepidocrocite and Goethite . . . . . . . . . . . . . . . . . . . 194
8.4.5 α/γ∗ Ratio . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
8.5 Summary. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
9 Synchrotron Radiation Study on Structure of Atmospheric
Corrosion Products Formed on Steel Surfaces
Hiroyuki Konishi, Masato Yamashita, Jun’ichiro Mizuki,
Hitoshi Uchida …………………………………………. 199
9.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
9.2 Composition of Protective Rust Layer Formed on
Weathering Steel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 200
9.3 Structural Study on the Protective Rust Layer using X-ray Absorption
Spectroscopy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201
9.3.1 X-ray Absorption Fine Structure Analysis . . . . . . . . . . . . . . 202
9.3.2 Sample Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203
9.3.3 Measurements and Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205
9.3.4 Structural Properties of the Protective Rust Layer . . . . . . . 212
9.4 In situ Observation of Corrosion Process in Wet/Dry Cycles . . . . . 213
9.4.1 Experimental Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 213
9.4.2 Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215
9.4.3 Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 219

Contents XIII
9.5 Summary. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 220
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221
10 Analysis of Iron Rusts by X-ray Diffraction and X-ray
Absorption Fine Structure Measurements
Takenori Nakayama, Tatsuo Ishikawa ………………………… 223
10.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223
10.2 Rust Analysis by X-ray Diffraction (XRD) . . . . . . . . . . . . . . . . . . . . . 224
10.2.1 Quantitative Measurement of Rust Composition . . . . . . . . . 224
10.2.2 Analysis of Crystallite Size of Rust Particle . . . . . . . . . . . . . 225
10.2.3 In-situ Observation of Oxidation and Reduction Processes
of Iron Rusts by Synchrotron Radiation . . . . . . . . . . . . . . . . 226

10.3 Rust Analysis by X-ray Adsorption
Fine Structure (XAFS). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
10.4 Approach of Artificial Rust Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . 229
10.4.1 Background of the Approach . . . . . . . . . . . . . . . . . . . . . . . . . . 229
10.4.2 Synthesis of Rust Particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232
10.4.3 Particle Morphology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232
10.4.4 Specific Surface Area . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
10.4.5 XRD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
10.4.6 Crystallite Size . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
10.4.7 Comparison of Effects of Metal Ions on Particle Size
and Crystallinity of Rusts. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
10.4.8 Comprehensive Comparison of Effects of Metal Ions . . . . . . 239
10.4.9 Mechanism for Emergence of Corrosion Resistance . . . . . . . 241
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242
11 Various Scale Analyses to Create Functioning Corrosion
Products
Masao Kimura, Tadashi Mizoguchi, Hiroshi Kihira, Michio Kaneko …. 245
11.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
11.2 Various Scale Analyses for Structures of Corrosion Products . . . . . 246
11.2.1 Ideal Structures of Iron Oxyhydroxides and Oxides. . . . . . . 246
11.2.2 Formation Process of Corrosion Products . . . . . . . . . . . . . . . 246
11.2.3 Surface of Corrosion Products in an Aquatic Media . . . . . . 250
11.3 Strategies for Preventing Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
11.3.1 Resisting Acidification Near the Solution/Metal Interface:
“pH-strategy” . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251

11.3.2 Shielding the Interface against Environments: “shielding-
strategy” . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252

11.4 Analytical Techniques of Corrosion
on Various Scales . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252
11.4.1 In situ Observation of Reactions near the Solution/Metal
Interface using Synchrotron Radiation . . . . . . . . . . . . . . . . . . 252

XIV Contents
11.4.2 M ̈ossbauer Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 254
11.5 Establishing pH-strategy through Analyses of Localized Corrosion
on Stainless Steel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257
11.5.1 Localized Corrosion of Stainless Steel. . . . . . . . . . . . . . . . . . . 257
11.5.2 Concentration of Metal Cations inside a Locally
Corroding Part . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257
11.5.3 Formation of Poly-Mo(O, OH)6 Octahedra . . . . . . . . . . . . . . 258
11.6 Establishing shielding-strategy through
Analyses of Protective Rust on Weathering Steel . . . . . . . . . . . . . . . 261
11.6.1 Protective Rust on Weathering Steel . . . . . . . . . . . . . . . . . . . 261
11.6.2 Polymerization of Fe(O, OH)6 Octahedra through
Wet and Dry Cycles. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261
11.6.3 Various Scale Analyses for Structures of Protective Rust . . 262
11.7 Combination of pH- and shielding-strategies through Analyses
of Protective Rust on Advanced Weathering Steel . . . . . . . . . . . . . . 266
11.7.1 Advanced Weathering Steel . . . . . . . . . . . . . . . . . . . . . . . . . . . 266
11.7.2 Polymerization of (Fe, Ni)(O, OH)6 Octahedra through Wet
and Dry Cycles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 266
11.7.3 Formation of Cation-exchanging Poly-(Fe, Ni)(O, OH)6 . . . 267
11.7.4 Various Scale Analyses of the Rust on the Advanced
Weathering Steel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 268
11.8 Summary. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 269
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 270
12 M ̈ossbauer Spectroscopic Study on Rust Formed
on Steel Surfaces
Takayuki Kamimura, Saburo Nasu ………………………….. 273
12.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 273
12.2 Importance of Rust in Corrosion Process
of Steel During Wet and Dry Cyclic Conditions . . . . . . . . . . . . . . . . 274
12.3 M ̈ossbauer Spectroscopy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 277
12.4 Investigation of Rust Formed on Weathering Steel and
Mild Steel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 282
12.5 Summary. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 288
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 288
Index …………………………………………………

 

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