ANNUAL REPORT2014

CORROSION RESEARCH
Materials Science and Engineering

Publishedby
THE CORROSION RESEARCH GROUPHOKKAIDO UNIVERSITY

No. 43i

For additional copies and more information, please write to the group members
Prof. M. Ueda: LABORATORY OF MATERIALS FOR SUSTAINABLE
ENGINEERING
Prof. H. Habazaki: INTERFACIAL ELECTROCHEMISTRY LABORATORY
Prof. R. O. Suzuki: LABORATORY OF ECO-PROCESSING

AFFILIATE MEMBERS
Prof. K. Azumi:
Assoc. Prof. K. Fushimi:
Assoc. Prof. M. Sakairi:
Faculty of Engineering, Hokkaido University
Kita 13, Nishi 8, Kita-ku, Sapporo 060-8628, Japanii

CURRENT ACTIVITIES and PRESENTATIONSLABORATORY OF MATERIALS FOR SUSTAINABLE
ENGINEERING ................................................................................................ 1
NTERFACIAL ELECTROCHEMISTRY LABORATORY ................................ 7
ECO-PROCESSING LABORATORY ...............................................................15

AFFILIATE MEMBERS

Prof. Dr. Kazuhisa Azumi ................................................................................ 27
Assoc. Prof. Dr. Koji Fushimi ........................................................................... 34
Assoc. Prof. Dr. Masatoshi Sakairi ................................................................... 40

ABSTRACT of PUBLICATIONSElectrorefining of Sodium in Sodium Bis(trifluoromethane)sulfonylimide andTetrabutylammonium Bis(trifluoromethane)sulfonylimide Mixture Ionic Liquids
for Metallic Sodium Recycling ........................................................................ 51
Observation of Three-Phase Interface during Hydrogen Electrode Reactions in
53
Unitized Regenerative Fuel Cell ....................................................................... 52
Output Characteristics of a Circular Cone Type Graphite Cathode for Al-Cl2 Fuel
Cells in AlCl3-EMIC Ionic Liquid ................................................................... 53
55
Improvement of Protective Polypyrrole Film for Corrosion of Zinc-Coated54
AZ91D Alloy ................................................................................................... 53
55
Influence of pH on the Synthesis and Properties of Polypyrrole on Copper from
53
55
iii
55

Phytic Acid Solution for Corrosion Protection ………………………………... 55
Effect of Benzotriazole(BTA) Addition on Polypyrrole Film Formation on
Copper and Its Corrosion Protection ............................................................... 56
53
Gas Sensing Properties of the Nanostructured Anodic Zr–W Oxide Film.....… 57
53
55
Morphological Control of Anodic Crystalline TiO2 Nanochannel Films for Use in58
Size-selective Photocatalytic Decomposition of Organic Molecules ….......... 53
In Situ X-Ray Absorption Spectroscopy Study of Sn Underpotential Deposition55
59
on Ni from Perchloric Acid ............................................................................. 55
53
Electrochemical Analysis of Hydrogen Membrane Fuel Cells with Amorphous
53
Zirconium Phosphate Thin Film Electrolyte ..................................................... 60
55
Fabrication of Superoleophobic Hierarchical Surfaces for Low-surface-tension
Liquids .............................................................................................................. 61
53
55
Formation-structure-properties of Niobium-oxide Nanocolumn Arrays via Self-53
62
organized Anodization of Sputter-deposited Aluminum-on-niobium Layers .... 55
Nanostructured Anodic-alumina-based Dielectrics for High-frequency Integral 55
53
Capacitors ......................................................................................................... 63
Characterization of Self-Assembled Monolayer on Anodized Aluminum by XPS,53
AFM and Low-Voltage SEM ............................................................................ 64
55
The Effects of Film Thickness and Incorporated Anions on Pitting Corrosion of
Aluminum with Barrier-type Oxide Films Formed in Neutral Borate and53
55
Phosphate Electrolytes ..................................................................................... 65
Highly Enhanced Corrosion Resistance of Stainless Steel by Sol-Gel Layer-by-55
66
Layer Aluminosilicate Thin Coatings .............................................................. 53
Efficient Growth of Anodic Films on Magnesium in Organic Electrolytes
53
Containing Fluoride and Water ........................................................................ 67
55
Mixed Proton Electron Conductivity of Calcium Chromate(V) Apatite .......... 68
53
55
53

iv
55
55

Electrochemical Properties of Heated Carbon Nanofibers for Lithium Ion
Capacitor .......................................................................................................... 68
Bulk Mixed Ion Electron Conduction in Amorphous Gallium Oxide Causes
53
Memristive Behavior ...................................................................................... 69
Effect of Sn2+ on Anodic Dissolution of Ni in Perchloric Acid ....................... 70
53
55
Fabrication of a Micro-Porous Ti-Zr Alloy by Electroless Reduction with a
Calcium Reductant for Electrolytic Capacitor Applications ............................ 71
53
55
Fabrication of Anodic Porous Alumina by Squaric Acid Anodizing ............... 72
53
55
Rapid Reduction of Titanium Dioxide Nano-particles by Reduction with a
Calcium Reductant ........................................................................................... 73
53
55
Fabrication of Anodic Nanoporous Alumina via Acetylenedicarboxylic Acid
Anodizing ............................................................................................ ............. 74
53
55
Fabrication of Anodic Porous Alumina via Anodizing in Cyclic Oxocarbon
Acids ..................................................................................................................... 75
53
55
Self-Ordering Behavior of Anodic Porous Alumina via
Selenic Acid Anodizing ………………………………....………...………....... 76
53
55
Growth Behavior of Anodic Oxide Formed by Aluminum Anodizing in Glutaric
and Its Derivative Acid Electrolytes ................................................................ 53
77
55
Ultra-High Density Single Nanometer-Scale Anodic Alumina Nanofibers
Fabricated by Pyrophosphoric Acid Anodizing ................................................55
78
53
Porous Anodic Oxide Films on Aluminum and Their Nanofabrication(Review) ............................................................................... ............................. 79
53
55
Multiphase Particle Simulation of Gas Bubble Passing through Liquid/LiquidInterfaces ............................................................................... ............................ 53
80
55
Numerical Analysis of Carbon Monoxide-Hydrogen Gas Reduction of Iron Ore
in a Packed Bed by an Euler-Lagrange Approach ........................................... 81
53
55
Stable Mesh-free Moving Particle Semi-implicit Method for Direct Analysis of

v

53
55
55

Gas-Liquid Two-Phase Flow ........................................................................... 82
Ionic Conduction of Oxygen and Calciothermic Reduction in Molten CaOCaCl2 ................................................................................................................. 53
83
Thermoelectric Analysis for Helical Power Generation Systems ………….… 84
53
55
Thermoelectric Analysis for Pai-type Thermoelectric Module with Tilted
53
Elements ........................................................................................................... 85
55
Thermoelectric Analysis for a Three-Dimensional
53
Power Generator in Helical …………………………………………………..... 86
55
Optimization of Module Shape in Thermoelectric Power Generation ............. 87
55
Light-Concentration Characteristic of Water Lens and its Application 53
toThermoelectric Generation .............................................................................. 53
88
Simulation of a thermoelectric module having parallelogram elements …....... 55
89
53
55
New n-type Silicide Thermoelectric Material
with High Oxidation Resistance …..………………………………………….. 90
53
55
Using a Water Lens for Light Concentration in Thermoelectric Generation .... 91
53
55
Effects of Nano Metal Coatings on Growth Kinetics of α-Al2O3 Formed on Ni50Al Alloy ...................................................................................................... 53
92
55
Prospect of Corrosion Resistive Aluminum Plating Process on Magnesium
Alloys ................................................................................................... ............ 55
53
93
Convection-dependent Hydrogen Permeation into a Carbon Steel Sheet ......... 94
53
55
Corrosion Behaviour of Ferrite and Austenite Phases on Super Duplex StainlessSteel in a Modified Green-death Solution ........................................................ 95
53
55
Growth and Degradation of Anodic Oxide Film on Titaniumin Sulphuric Acid
Observed by Ellipso-microscopy ..................................................................... 53
96
55
Grain-dependent Passivation of Iron in Sulfuric Acid Solution......................... 97
53
55

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53
55

The Corrosion Resistance and Passive Film Compositions of 12% Cr and 15% Cr
ODS Steels in Nitric Acid Media ................................................................... 98
The Surface Characterization and Corrosion Resistance of 11%
CrFerritic/Martensitic and 9-15% Cr ODS Steelsfor Nuclear Fuel Reprocessing
53
Application ............................................................................... ........................ 99
Effect of Metal Cations on Corrosion Behavior and Surface Film Structure of55
the A3003 Aluminum Alloy in Model Tap Waters .........................................100
53
Evaluation of Metal Cation Effects on Galvanic Corrosion Behavior of the
53
A5052 Aluminum Alloy in Low Chloride Ion Containing Solutions by
55
Electrochemical Noise Impedance ................................................................ 101
Line Shaped Porous Type Anodic Oxide Film Formation on Aluminumby Sf- 55
MDC with Coated Pt Wire Electrode ............................................................. 102
53
Evaluation of Metal Cation Effects on Galvanic Corrosion of Aluminum Alloys
53
in Low Chloride Ion Containing Solutions with Electrochemical Noise ….… 103
55
Oxide Films on Nickel-base Alloys in Water at 360 ˚C
53under PWR Environment ………………………………………………………… 104
55
Electrochemical Noise Analysis on Modified 13%Cr Stainless Steels in Sour
53
Environments under Stress ............................................................................ 105
55
Metal Cation Effects on Galvanic Corrosion Behavior of 2024 Aluminum Alloywith Electrochemical Noise ............................................................................ 106
53
55
53
55
55

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CURRENT ACTIVITIES and PRESENTATIONSLABORATORY OF MATERIALS FOR SUSTAINABLE
ENGINEERING
Prof. Dr. Mikito Ueda
TEL / FAX: +81-11-706-7813
E-mail: mikito@eng.hokudai.ac.jp
Assoc. Prof. Dr. Hisayoshi Matsushima
TEL / FAX: +81-11-706-6352
E-mail: matsushima@eng.hokudai.ac.jp
Academic Researcher Dr. Toshiaki Ohtsuka
TEL / FAX: +81-11-706-6351
E-mail: ohtsuka@eng.hokudai.ac.jp
Secretary Mrs. Mari Takagi
TEL/FAX: +81-11-706-7813
E-mail: mtakagi@eng.hokudai.ac.jp

Students
C. Namekata, R. Nakanishi, Y. Yasui, S. Shibuya, S. Honda, A. Tsuruta, K.
Sato, Y. Kohno, C. Katayama, K. Yamada, K. Kikui

Assist. Prof. Hisayoshi Matsushima in Yamanashi University was promoted
to the Assoc. professor of our laboratory from April 2014. Mrs. Takagi is working
as a secretary of the laboratory from August 2014.
Our research activities are concerned with molten salts electrolysis, waterelectrolysis, surface sciences about metal surface, and fuel cell.
Current topics on research are in the following:(1) Electrorefining of Na for recycling of used Na-S secondary batteries
To develop electrorefining process of metallic Na from the used Na-S battery.
There is no electrorefining process of sodium in the industrial scale. We were1

investigated NaFSI-TEATFSI ionic liquid as candidate of the electrolytic melt. In
the electrorefining experiment for more than 20 hours, 99.98% pure Na was
obtained from simulated Na in used Na-S battery.
(2) Electrodeposition of Al-Zr alloys in chloride molten salt
To improve the corrosion resistance of Al in chloride solutions,electrodeposition of Al-Zr alloys of various compositions was carried out at 448 K
by constant potential control in AlCl3-NaCl-KCl molten salt containing ZrCl4. The
electrodeposition was performed by constant potential electrolysis from -1.4 to 1.6 V.
(3) Development of Al-Cl2 cell in ionic liquid
To develop an aluminum-chlorine cell, an electrochemical cell consisting ofan aluminum anode and a graphite cathode was developed and evaluated in EMICAlCl3 ionic liquid.
The relationship between current density and cell voltage in the cell showed
an almost linear relation. The output characteristics of the cell depend on theconfiguration of the graphite cathode, the current density with a circular cone type
cathode at 0.5 V was about 40 % better than that of a cylindrical type graphite
cathode.
(4) Investigation of Li metal surface by surface observation
Li metals in some non-aqueous solution were evaluated by surface
observation. Dendrite growth on the Li surface was observed in several kinds ofsolvents.
(5) In-situ observation of electrochemical interfacial phenomena by Video-AFM
We have developed the atomic force microscopy with fast scanning rate (VideAFM) and in-situly observed the electrochemical nucleation/dissolution. At thepresent, Cu electrodeposition/dissolution on HOPG substrate has been
investigated in aqueous sulfuric acid solution. The video-AFM demonstrated that
the Cu deposits was started at the convex points and defects on the surface.

2(6) Hydrogen isotope separate by fuel cell
We are exploring the possibility of hydrogen isotope separation by using PEM
fuel cell. The kinetic parameters of hydrogen or deuterium oxidation reaction(HOR or DOR) are investigated by rotating disc electrode (RDE). The separation
factor of D/H during PEM operation will be measured by quadrupole mass
spectroscopy (Q-mass).
(7) NIR study for Nafion membrane below freezing temperature
We in-situly apply near infrared spectroscopy (NIR) for Nafion membrane
below freezing temperature. Simultaneously, we carry out the impedance
measurement in order to research the conductivity mechanism of the polymer.

Other Activities
Prof. Ueda was invited 2014 ECS and SMEQ Joint International Meeting, Cancun,
Mexico, October5-9, 2014 and presented keynote lecture entitled by"Electrorefining of Na in Hydrophobic Ionic Liquid".
Prof. Ueda attended 2nd International Conference on Ionic Liquids in Separation and
Purification Technology, and present paper entitled by "Electrorefining of Na in
TBATFSI-NaTFSI ionic liquids", Toronto, Canada, June 29- July 2, 2014.

Presentations
T. Teshima, M. Ueda, T. Ohtsuka, Electrodeposition of Al-Zr alloy in AlCl3- NaClKCl containing ZrCl 4, Winter Meeting of Hokkaido Branch of Jpn. Inst. Metals
and ISIJ, Sapporo, January 23-24, 2014.
S. Honda , A. Hyono, M. Ueda, Electrodeposition of Al-Sn-Cu alloy in AlCl3NaCl-KCl molten salt containing SnCl2 and CuCl2, Winter Joint Meeting of
Hokkaido Branch of Chemistry-related Societies, Sapporo, January 28-29, 2014.
J. Nunomura , A. Hyono, M. Ueda, T. Ohtsuka, Effect of alloy elements inaluminum anode for Al-Cl2 cell characteristics, Winter Joint Meeting of Hokkaido
Branch of Chemistry-related Societies, Sapporo, January 28-29, 2014.

3

S. Shibuya, A. Hyono, T. Ohtsuka, M. Ueda, The in-situ Raman measurement of
the lithium metal electrode surface during the charging and discharging inpropylene carbonate, The 129th Meeting of The Surface Finishing Society, Tokyo
University of Science, Chiba, March 13-14, 2014.
S. Honda, A. Hyono, M. Ueda, Electrodeposition of Al-Sn-Cu alloy from low
temperature chloride molten salt using the constant potential electrolysis andconstant potential pulse electrolysis, The 81st meeting of ECSJ, Kansai University,
Osaka, March 29-31, 2014.
H. Matsushima, Research for electrochemical interfacial phenomena targeting forhydrogen energy society, Material Seminar, Sapporo, April 25, 2014.
Chika Namekata, Toshiaki Ohtsuka, and Mikito Ueda, Effect of Additive for
Smooth Al Electroplating in AlCl3-EMIC Ionic Liquid, Anodizing Science andTechnology 2014, Sapporo, June 4-6, 2014.
Hiroki Murakoshi, Kazuhisa Azumi, and Mikito Ueda, Optimization ofElectrodeposition Al on Mg Alloy from the Molten Salt Bath, Anodizing Scienceand Technology 2014, Sapporo, June 4-6, 2014.
Koji Fushimi, Kazunori Kurauchi, Takayuki Nakanishi, Yasuchika Hasegawa, andMikito Ueda, Ellipso-microscopic Imaging of Anodized Titanium Surface under
UV-light Irradiation, Anodizing Science and Technology 2014, Sapporo, June 4-6,
2014.
Mikito Ueda, Ryuich Inaba, and Toshiaki Ohtsuka, Electrorefining of Na in
TBATFSI-NaTFSI ionic liquids, 2nd International Conference on Ionic Liquids in
Separation and Purification Technology, Toronto, Canada, June 29- July 2, 2014.
Y. Yasui, A. Hyono, H. Matsushima, T. Ohtsuka, M. Ueda, Evaluation of as anelectrolyte of NaFSI-TEATFSI mixed ionic liquid for Na electrorefining, Summer
meeting 2014 of Hokkaido branch of The Chemical Society of Japan, Hokkaido,
Tomakomai National College of Technology, July 12, 2014.
Mikito Ueda, Materials science study using molten salt and ionic liquid, Summer
meeting 2014 of Hokkaido branch of The Chemical Society of Japan, Hokkaido,

4

Tomakomai National College of Technology, July 12, 2014.
Mikito Ueda, Aluminum alloys plating using molten salts and ionic liquid, The
130th Meeting of The Surface Finishing Society, Kyoto University, Kyoto,
September 22-23, 2014.
C. Namekata, A. Hyono, H. Matsushima, T. Ohtsuka, M. Ueda, Effect ofelectroplating thickness for the surface smoothness in the Al electroplating fromionic liquid, The 130th Meeting of The Surface Finishing Society, Kyoto
University, Kyoto, September 22-23, 2014.
H. Murakoshi, K. Azumi, M. Ueda, Optimization of Al plating from the molten saltbath for AZ31 alloy, The 130th Meeting of The Surface Finishing Society, Kyoto
University, Kyoto, September 22-23, 2014.
H. Matsushima, In-situ observation study for relationship between hydrogen
evolution and metal interface, Fall meeting of the Japan institute of metals andmaterials, Nagoya, September 24-26, 2014.
Y. Yasui, A. Hyono, H. Matsushima, T. Ohtsuka, M. Ueda, Electrodeposition of
Na on Fe cathode in Na electrorefining, Meeting of ECSJ 2014 , Hokkaido
University, Sapporo, September 27-28, 2014.
A. Tsuruta, M. Ueda, H. Date, T. Fujii, Electrodeposition of Si in TFSI ionicliquids, Meeting of ECSJ 2014 , Hokkaido University, Sapporo, September 2728, 2014.
S. Shibuya, A. Hyono, H. Matsushima, M. Ueda, Kinetic study of isotope
separation in the hydrogen electrode reaction, Meeting of ECSJ 2014 , Hokkaido
University, Sapporo, September 27-28, 2014.
Mikito Ueda, Electrorefining of Na in Hydrophobic Ionic Liquid, 2014 ECS and
SMEQ Joint International Meeting, Cancun, Mexico, October5-9, 2014.
R. Nakanishi, A. Hyono, H. Matsushima, M. Ueda, Al electrodeposition to porous
Ni in EMIC-AlCl3 ionic liquid, The 46h Symposium on Molten Salt Chemistry,
Kazusa Akademia Hall, Chiba, November 13-14, 2014.

5

Facilities and Capabilities
Ellipsometer: Rotating-analyzer type of automated ellipsometer with 632.8 nm
wavelength of light and null-method ellipsometer for multiple-angle-of-incidence
measurement.
Potential Modulation Reflectance: Wavelength region from 350 to 800 nm
Raman Scattering Spectrometer: Bunko Keiki, single type of spectrometerequipped by high sensitive CCD.
FT-IR Spectrometer: JASCO FT/IR 4200 equipped with MCT detector, IR-RAS
apparatus and IR microscopy system.
QCM system for in-situ gravimetry of surface layer on metals.
Electrochemical AC Impedance: NF Circuit Design 5020 FRA and 5095 FRA
equipped with a specially designed potentiostat.
ICP atomic emission spectrometer: Thermo i-CAP 6000.
Carl Fischer moisture measuring system: Metrohm 852 titrando.
Evaporator: Eyela SB1100.
Electrochemistry apparatuses.
Optical Microscopy.
Electrochemical Corrosion Rate Monitor System.
Molten salt ion-exchange apparatus for glass.
Luminescence apparatus for thin surface layer equipped with He-Cd UV laser.
Video scanning rate Atomic Force Microscopy (Video-AFM).
Quadrupole Mass Spectroscopy (Q-Mass): ULVAC Quless CGM-052.
Rotating Disc Electrode (RDE) system.
Near Infrared Spectrometer: Ocean optics NIR256-2.1

6

INTERFACIAL ELECTROCHEMISTRY LABORATORY
Prof. Dr. Hiroki Habazaki
Tel./Fax: +81-11-706-6575
E-mail: habazaki@eng.hokudai.ac.jp
Assoc. Prof. Dr. Yoshitaka Aoki
Tel./Fax: +81-11-706-6752
E-mail: y-aoki@eng.hokudai.ac.jp
Assist. Prof. Dr. Etsushi Tsuji
Tel./Fax: +81-11-706-6736
e-tsuji@eng.hokudai.ac.jp

Visiting Professor
Prof. Emeritus Dr. Masahiro Seo
TEL./FAX: +81-11-706-6735
E-mail: masaseo@eng.hokudai.ac.jp

Students
Y. Konno, K. Shahzad, H. Takano, H. Ogata, K. Nakayama, , F. Kataoka, K.
Kikutani, T. Kimura, C. Kura, T. Yamasaki, T. Hiraga, K. Kobayashi, S.
Kobayashi, H. Noda, S. Matsuura, Y. Okazaki, T. Kobayashi, T. Kuroda, R.
Sakashita, R. Tomizawa

The research activities of the laboratory are directed towards the developmentof advanced oxide films and nanomaterials utilizing anodizing process, sol-gel
process and PVD for possible applications including novel fuel cells, air batteries,
photovoltaic cells, corrosion protection, self-cleaning surfaces and capacitors. We
are also interested in surface analytical techniques with nanoscale resolution for abetter understanding of the interfacial phenomena of metal and semiconductor
electrodes in relation to electrochemical devices for energy storage and conversion,
corrosion, passivation and surface finishing.

7Current topics on research are in the following:(1) Intermediate-temperature fuel cells
We successfully fabricated gas-tight silicate and phosphate nanofilms, whichshow efficient proton conductivity even in dry atmosphere at intermediate
temperatures (200-400ºC). Utilizing the proton-conducting nanofilms as anelectrolyte membrane, we designed a hydrogen membrane fuel cells (HMFCs). In
HMFCs, palladium foil was used as a hydrogen-permeable anode and we
succeeded power generation. We also found that the ZrO2-WO3-SiO2 films formedby anodizing of magnetron-sputtered Zr-W-Si alloys reveal high proton
conductivity even below 200ºC.
(2) Tailoring of self-organized porous anodic oxides on various metals
Recently, we have found that phosphate-glycerol solution at elevatedtemperature is a new electrolyte to form self-organized porous anodic films onvarious valve metals. We have already successfully developed self-organizedporous anodic films on titanium, niobium and aluminum in the hot phosphateglycerol electrolyte. For titanium, we succeeded to obtain mesoporous crystalline
anatase films without post annealing. In addition, using organic electrolytes
containing fluoride ions, self-organized nanoporous anodic films have beensuccessfully developed on iron and stainless steel. The growth behavior and theirproperties have been examined in detail.
(3) Fabrication of superhydrophobic and superoleophobic surfaces
One of the important factors to control the surface wettability of solidmaterials is surface geometry. Hierarchical porous surface morphology is ofparticular importance to obtain superhydrophobic surfaces together with surface
energy of solid materials. Further precise control of the surface geometry resulted
in the formation of superoleophobic surfaces, on which oil droplets were readilyrolled off. Utilizing porous anodic films, we developed hierarchical surfaces on
aluminum and aluminum alloys and obtained superolephobic surfaces after coatingwith a fluoroalkyl monolayer, which had the lowest surface energy.

8(4) Novel dielectric films formed by anodizing
One of the important practical applications of the anodic films on valve metals
is dielectric in electrolytic capacitors. We have examined dielectric properties of
the anodic films formed on a range of novel valve metal alloys. Detailed
investigations on the significant enhancement of capacitance by forming
nanocomposite anodic films, consisting of nanocrystalline tetragonal ZrO2 phaseand an amorphous matrix, have been conducted.
Other activities
Prof. H. Habazaki presented invited lectures entitled “Formation of ZrO 2-based
Nanocomposite Anodic Films with High Capacitance” at the 2nd International
Symposium on Anodizing Science and Technology (AST2014), which was held on
4-6 June 2014 at Sapporo, “Electrochemical fabrication of micro-/nano-dual scalerough surfaces for super-repellency for various liquids” at 10th International
Symposium on Electrochemical Micro & Nanosystem Technologies, which washeld on 5-8 November 2014, Okinawa Convention Center, Ginowan, and “Ptsupported Platelet Carbon Nanofibers for Oxygen Reduction Reaction” at 5th
Symposium on Academic Exchange and Collaborative Research CompetenceCenter for Materials & Processes, ETH Zürich (MaP) and Graduate School ofEngineering, Hokkaido University, held on 27-28 November 2014, at ETH Zurich.
Associate Prof. Y. Aoki presented invited lectures entitled “Reversible Redox
Behavior of NdCrO4 by Insertion/Desertion of Proton through Gas-Solid Reaction”
at Solid State Proton Conductors-17 (SSPC-17), which was held on 14-19 Sept.
2014 at Seoul, Korea, and “Joint Japan-German research using the ‘Frenchelement’ Gallium for next generation electronics” at German JSPS Meeting in
Chitose, which was held on 17 May at Chitose Institute of Science andTechnology, Chitose.
Assist. Prof. E. Tsuji presented invited lectures entitled “Photoelectrochemical
Applications of Crystalline TiO 2 Nanochannel Films Anodized in Fluoride-freeElectrolytes” at International Conference of Smart Systems Engineering 2014,
which was held on 15-17 October 2014 at Yonezawa, Japan.

9

Presentations
C. Kura, Y. Aoki, E. Tsuji, H. Habazaki, “Resistive Switching Behavior of
Amorphous TiOx Thin Films prepared by Reactive Sputtering Process”, 1stInternational Symposium on “Ambitious Leader’s Program for Fostering Future
Leaders to Open New Frontiers in Material Science”, March 7, Hokkaido
University, Hokkaido, 2014.
Masahiro Seo, Hiroki Habazaki, Masayuki Inaba, Mitsutoshi Yokomizo, Takumi
Wakabayashi, Takenori Nakayama, “In-situ X-ray absorption spectroscopy of Sn
adsorption structure on Ni”, Zairyo-to-Kankyo 2014, May 18-20, Tokyo, 2014.
Y. Aoki, R. Nonaka, E. Tshuji, H. Habazaki, “Hydrogen membrane fuel cell basedon amorphous electrolyte thin films”, 2014 E-MRS Spring Meeting, May 26-30,
Lille, France, 2014.
F. Kataoka, E. Tsuji, Y. Aoki, S. Nagata, H. Habazaki, “Formation of Anodic Films
on Magnesium in Ethylene Glycol-H2O Electrolytes Containing Fluoride”, 2ndInternational Symposium on Anodizing Science and Technology, June 4 -6,
Chateraise Gateaux Kingdom Sapporo Hotel & Spa Resort, Sapporo, 2014.
Kohei Kobayashi, Etsushi Tsuji, Yoshitaka Aoki, Shinji Nagata and Hiroki
Habazaki, “Characterization of Anodic Films Formed on Ti-Zr Alloys”, June 4- 6,
Chateraise Gateaux Kingdom Sapporo Hotel & Spa Resort, Sapporo, 2014.
T. Yamasaki, E. Tsuji, Y. Aoki S.-G Park and H. Habazaki “Pt/Platelet Carbon
Nanofibers Synthesized by Liquid Phase Carbonization in Porous Anodic Alumina
Templates for Oxygen Reduction Reaction”, June 4 -6, Chateraise Gateaux
Kingdom Sapporo Hotel & Spa Resort, Sapporo, 2014.
Yoshiki Konno, Etsushi Tsuji, Yoshitaka Aoki, Toshiaki Ohtsuka, Hiroki
Habazaki, “Formation of Composite Coatings of Porous Anodic
Oxide/Polypyrrole on Iron”, June 4-6, Chateraise Gateaux Kingdom Sapporo Hotel& Spa Resort, Sapporo, 2014.
Y. Nakayama, E. Tsuji, Y. Aoki, and H. Habazaki, “Potentiodynamic Study of10the Formation of Anodic Alumina Films in Oxalic Acid Electrolyte”, June 4 -6,
Chateraise Gateaux Kingdom Sapporo Hotel & Spa Resort, Sapporo, 2014.
Soo-Gil Park, Jin-Kwon Choi, Hong-Il Kim, Dal-Woo Shin, Sung-Han Kim,
Moon-Su Lee, Hiroki Habazaki, “Control the Pore Size of AAO Templates forElectrochemical Capacitors”, June 4-6, Chateraise Gateaux Kingdom Sapporo
Hotel & Spa Resort, Sapporo, 2014.
Shiki Matsuura, Etsushi Tsuji, Yoshitaka Aoki, and Hiroki Habazaki, “Cyclic
Voltammometric Study of the Formation of Crystalline TiO2 Mesoporous Anodic
Films in Hot Phosphate/glycerol Electrolytes”, June 4-6, Chateraise Gateaux
Kingdom Sapporo Hotel & Spa Resort, Sapporo, 2014.
Khurram Shahzad, Etsushi Tsuji, Yoshitaka Aoki, Shinji Nagata, Hiroki Habazaki.,“On the Influence of Electric Field on Dissolution Rate of Anodic Films on Iron”
June 4-6, Chateraise Gateaux Kingdom Sapporo Hotel & Spa Resort, Sapporo,
2014.
Katsutoshi Nakayama, Etsushi Tsuji, Yoshitaka Aoki, and Hiroki Habazaki,“Fabrication of Superoleophobic Hierarchical Surfaces on Aluminum by Chemical
Etching and Anodizing”, June 4-6, Chateraise Gateaux Kingdom Sapporo Hotel &Spa Resort, Sapporo, 2014.
Y. Konno, E. Tsuji, Y. Aoki, T. Ohtsuka, H. Habazaki, “Removal of fluoride
species from the porous anodic oxide – polypyrrole composite coating on iron”,
The 3rd Fronthier Chemistry Center International Symposium “Chanllenges at the
Frontier of Chemical Sciences”, June 13-14, Hokkaido Univ., Sapporo, 2014.
K. Shahzad, E. Tsuji, Y. Aoki, S. Nagata, H. Habazaki, “Effect of sweep rate on
formation of nanostructured iron oxide films under potentiodynamic anodizing”,
The 3rd Fronthier Chemistry Center International Symposium “Challenges at the
Frontier of Chemical Sciences”, June 13-14, Hokkaido Univ., Sapporo, 2014.
T. Kimura, T. Yano, E. Tsuji, Y. Aoki, H. Habazaki, “Oxidation of type 430
stainless steel covered with aluminosilicate thin coating at elevated temperatures”,
Int. Symp. on High-temperature Oxidation and Corrosion (ISHOC 2014), June1123-27, Hakodate Kokusai Hotel, Hakodate, 2014.
Y. Aoki, “Bulk Mixed Ion Electron Conduction in Amorphous Gallium Oxide
Causes Memristive Behaviour”, 7th Nagoya Univ.-Tsinghua Univ.-Toyota Motor
Corp.-Hokkaido Univ. Joint Symposium ― Materials Science and Nanotechnology
for the 21st Century ―, 21-24 July, Hokkaido Univ., Sapporo, 2014.
C. Kura, Y. Aoki, E. Tsuji, H. Habazaki, “Resistive switching of HighlyNonstoichiometric GaOx Thin Films with Low valence state Ga + cation having(4s)2 lone pair electrons”, 7th Nagoya Univ.-Tsinghua Univ.-Toyota Motor Corp.Hokkaido Univ. Joint Symposium ― Materials Science and Nanotechnology forthe 21st Century ―, 21-24 July, Hokkaido Univ., Sapporo, 2014.
T. Yamasaki, E. Tsuji, Y. Aoki, S-G. Park, H. Habazaki, “Highly Dispersed Pt
Deposition on Platelet Structure Carbon Nanofiber Synthesized by Liquid Phase
Carbonization”, 7th Nagoya Univ.-Tsinghua Univ.-Toyota Motor Corp.Hokkaido Univ. Joint Symposium ― Materials Science and Nanotechnology forthe 21st Century ―, 21-24 July, Hokkaido Univ., Sapporo, 2014.
H. Takano, K. Izumiya, N. Kumagai, H. Habazaki, K. Hashimoto,“Characterization and catalytic properties of Ni/Ca-doped ZrO2 for CO2
methanation” 7th Nagoya Univ.-Tsinghua Univ.-Toyota Motor Corp.-Hokkaido
Univ. Joint Symposium ― Materials Science and Nanotechnology for the 21stCentury ―, 21-24 July, Hokkaido Univ., Sapporo, 2014.
E. Tsuji, Y. Taguchi, Y. Aoki, H. Habazaki, “Size-selective Photocatalytic
Decomposition of Organic Molecules Using Anodic Crystalline TiO 2 Mesoporous
Films”, 20th International Conference on Photochemical Conversion and Storageof Solar Energy, July 27-August 1, 2014, Berlin, Germany, 2014.
F. Di Franco, A. Zaffora, M. Santamaria, F. Di Quarto, E. Tsuji, H. Habazaki,“Tuning of solid state properties of Al-Ta mixed oxides”, 65th Annual Meeting of
the International Society of Electrochemistry, August 31-September 5, 2014,
EPFL, Lausanne, 2014.
H. Habazaki, F. Kataoka, E. Tsuji, Y. Aoki, S. Nagata, “Efficient Growth of12Anodic Films on Magnesium in Fluoride-containing Electrolytes”, 65th Annual
Meeting of the International Society of Electrochemistry, August 31 -September 5,
2014, EPFL, Lausanne, 2014.
M. Seo, H. Habazaki, M. Inaba, M. Yokomizo, T. Wakabayashi, T. Nakayama,“Inhibition Effect of Sn2+ on Corrosion of Ni and Sn Adsorption Structure”, 65th
Annual Meeting of the International Society of Electrochemistry, August 31 September 5, 2014, EPFL, Lausanne, 2014.
E. Tsuji, Y. Taguchi, Y. Aoki, H. Habazaki, “Nanostructural Control andPhotocatalytic Application of Anodic TiO2 Nanochannel Films”, 10th International
Symposium on Electrochemical Micro & Nanosystem Technologies, 5-8
November, Okinawa Convention Center, Ginowan, 2014.
T. Yamasaki, E. Tsuji, Y. Aoki, S.G. Park, H. Habazaki, “Influence ofGraphitization Degree on the Durability of Pt/Platelet Carbon Nanofibers
Electrocatalysts for Oxygen Reduction”, 10th International Symposium on
Electrochemical Micro & Nanosystem Technologies, 5-8 November, Okinawa
Convention Center, Ginowan, 2014.
K. Kikutani, Y. Aoki, E. Tsuji, H. Habazaki, “Proton conductivity of amorphouszirconium phosphate thin film formed on various substrates”, 10th International
Symposium on Electrochemical Micro & Nanosystem Technologies, 5 -8
November, Okinawa Convention Center, Ginowan, 2014.
C. Kura, Y. Aoki, E. Tsuji, H. Habazaki, “Fabrication of TiN1-x membranes on
porous oxide substrate by reactive RF sputtering”, 2nd International Symposiumof Ambitious Leader’s Program Fostering Future Leaders to open new Frontiers inMaterials Science: Ambition Across the Disciplines, 11-12 December, Hokkaido
University, Hokkaido, 2014.

Facilities and Capabilities
DC and RF magnetron sputtering: Shimadzu SP-2C, suitable for preparation ofvarious metallic thin films as well as oxide and nitride films.

13

FT-IR spectrometer: Jasco FT-IR350, equipped with DR and RAS attachments.
Ultramicrotomy: RMC MT-7 and PT-X, suitable for the preparation of electrontransparent TEM sections.
AFM: SII SPA-400 system with conductive AFM mode as well as contact andtapping modes.
Impedance analyzer: Solartron 1260, measureable in the frequency range ofHz to 32 MHz.

10

Contact angle meters: Kyowa Interface Science, Dropmaster system, to evaluate
superhydrophobicity solid surface.
Q-mass: Balzers Quadstar421 system for mass analysis of gases with mass
number of less than 200.
Tribometer: CSM pin-on-disk tribometer for wear and friction characterizationof coated materials

14

ECO-PROCESSING LABORATORY
Prof. Dr. R. O. Suzuki
Tel.:+81-11-706-6339 Fax.:+81-11-706-7882
E-mail:rsuzuki@eng.hokudai.ac.jp
Assoc.Prof. Dr. T. Kikuchi
Tel.:+81-11-706-6340 Fax.:+81-11-706-6341
E-mail:kiku@eng.hokudai.ac.jp
Assist. Prof. Dr. S. Natsui
Tel.:+81-11-706-6340 Fax.:+81-11-706-6342

Foreign Researchers
Dr. Xiang-Ning MENG

Technical Staffs
M. Kitamura, H. Noguchi, E. Takahashi, M. Tanaka, A. Yamase

Students
M. Baba, K. O. Ito, O. Nishinaga, R. Ishida(deceased), T. Wakamatsu,
J. Kawashima, H. Takai, D. Nakajima, H. Hada, F. Matsuura,
S. Akiya, S. Oki, N. Suzuki, A. Takenaga, R. Nashimoto

Prof. Ryosuke O. Suzuki merged as the professor of the laboratory of Ecoprocessing from Kyoto University on March 2006. He studies the non-ferrous
metallurgy based on the molten salt electrolysis. His research activities are directed
to design the economical and environment-friendly processes for materials
production at high temperatures. The extraction metallurgy of the refractory metals
such as Nb and Ta, and of valve metals such as Ti, V and Zr, serves many topics
when the electrolysis of CaO in the molten CaCl2 is applied. The electrolysis of
CO2 gas is one of the extreme cases in oxide decomposition. The thermoelectric
power generation is designed from the view of material design and heat exchange.

15

Dr. Kikuchi joined as an associate professor from laboratory of interface
microstructure analysis on May 2010, and he began to study the micro- and nanostructure fabrication by electrochemical techniques such as anodizing,
electrochemical etching, and electrodeposition. Electroless calcium reduction oftitanium, zirconium, neodymium, and iron oxides in calcium chloride molten salt
at high temperature was also investigated for novel electronic device fabrication
and recycling of these metals.
Dr. Natsui joined as an assistant professor from Tohoku University on April
2013. His research activities are directed to design the low-carbon ferrous
metallurgy by using current numerical simulation technology such as discreteelement method, its coupling to CFD, and particle based hydrodynamics. And hebegan to develop the rapid electro-reduction system by emulsified molten salt at
high temperature.

Current topics on corrosion research are in the following:(1) Molten salt electrolysis of CaCl2
Reduction of the oxides of Ti, Nb and Ta are studied, when the CaO dissolvedin the molten CaCl2 is electrochemically decomposed to form metallic calcium. A
low oxygen potential produces the metallic powders at the cathode. The reduced
metallic powder is prepared directly from the oxides. The mechanism of this
proposal is examined from the electrochemistry and thermodynamics. CO2 gas
reduction catches the current interests in the morphology of precipitated carbon
particles.
(2) Micro- and Nano-structure fabrication by anodizing
Anodic porous alumina has been widely investigated as a nanostructure templatein various nano-applications. The nano-morphology of porous alumina is limitedby the narrow range of electrolyte species used for anodizing. Therefore, thediscovery of additional electrolytes would greatly expand the applicability ofporous alumina. We have been working on new electrolytes, such as selenic, squaric,
croconic, rhodizonic, acetylenedicarboxylic, ketoglutaric, and acetonedicarboxylicacid, for anodic porous alumina fabrication. Our novel16

anodic porous alumina can be used as a nanotemplate for various nanostructures in
100-, 10-, and sub-10-nm-scale manufacturing. In addition, ultra-high density
single nanometer-scale anodic alumina nanofibers consisting of an amorphous,
pure aluminum oxide were successfully fabricated via pyrophosphoric acidanodizing. The aluminum surface covered by the anodic alumina nanofibers
exhibited ultra-fast superhydrophilic behavior, with a contact angle of less than 1°,
within 1 second.
(3) Low-carbon ferrous metallurgical design
In a ferrous metallurgical process, multiphase flow plays an important role inincreasing the efficiency by stirring liquid mechanically or by injecting a gas.
Owing to the difficulty of direct observation in a high–temperature system or real
furnace experiment, numerical analysis is useful and studied. We presents a newparticle–based simulation scheme for gas–liquid flow. We improved the numericalstability, which is generally a problem with the particle method, and verified themodel’s accuracy for fundamental gas–liquid flow analysis. This scheme is also
applicable to phenomena in an actual process that includes many dispersal phases.
Other activities(4) Thermoelectric power generation
An optimization of the thermoelectric generation is mathematically designed forthe highest output. This work links with energy harvesting to conduct theelectrolysis. The utilization of solar energy is challenged using cheap materials
such as water.
(5) Electro-reduction in suspended molten salt
The electrochemical reduction of metal oxides is an important process in active
metal production. The OS process has revolutionised molten salt electrolysis;
however, it still has diffusion and oxide rebuild-up issues. We attempted theelectro-reduction in suspended molten salt with gas flow. This approach expects
increasing reduction rate and eliminates some of these issues.
Prof. Suzuki made the keynote lecture on Production of Pure Ti Powder at the17

4th International Round Table on Titanium Production in Molten Salts held at
Shanghai University. Dr. Kikuchi made the invited lectures at the 31th Anodizing
Research Society Conference and the Autumn Meeting of Electrochemical Societyof Japan.
The following foreign scientists visited this laboratory: Prof. Kevin C.-W. Wu(Taiwan), Dr. Sorapong Pavasupree (Thailand), Prof. Frank F. S. Shieu (Taiwan).
Dr. X.-N. Meng retuned to Northeastern University, China, after working for 2
years as JSPS postdoctoral fellow.

Presentations
Anodizing in etidronic acid solution and their structural color generation; O.
Nishinaga, T. Kikuchi, S. Natsui and R. O. Suzuki : The 31th Anodizing ResearchSociety Conference, Oi-machi, Kanagawa, Japan, Nov., 2014.
Effect of electrolyte species on the growth behavior of anodic porous alumina; T.
Kikuchi : ibid.
Carbon Recycling by Electrochemical decomposition of CO2 in high-temperature
LiCl-KCl molten melt; S. Natsui : POWTEX TOKYO 2014 (The 20th
International Powder Technology Exhibition Tokyo), 27 Nov., 2014, Tokyo Big
Sight, Japan.
CO2 gas enrichment by the decomposition of CO2 gas in CaCl2-CaO molten salt;
F. Matsuura, H. Hada, T. Wakamatsu, S. Natsui, T. Kikuchi and R. O. Suzuki : The
46th Symposium on Molten Salt Chemistry, 13-14 Nov., 2014, Kazusa Academia
Hall, Kisarazu, Chiba, Japan.
Reduction of titanium oxide and evolution of anode gas by electrolysis in CaCl 2CaO molten salt; H. Hada, H. Noguchi, S. Natsui, T. Kikuchi and R. O. Suzuki :ibid.
Electrochemical measurement and direct observation of CO2 decomposition
behavior in LiCl-KCl melt; S. Natsui, M. Kitamura, T. Wakamatsu, T. Kikuchi and
R. O. Suzuki : ibid.

18

CO2 decomposition behavior by electrolysis in LiCl-Li2CO3 molten salt; T.
Wakamatsu, F. Matsuura, M. Kitamura, S. Natsui, T. Kikuchi and R. O. Suzuki :ibid.
Reduction of CaTiO3 by electrolysis in the molten salt (CaCl2-CaO) and cathodeshape; H. Noguchi, H. Hada, S. Natsui, T. Kikuchi and R. O. Suzuki : ibid.
Production of Pure Ti Powder from CaTiO3 Using Electrolysis in CaCl2-CaO Melt;
R. O. Suzuki : The 4th International Round Table on Titanium Production in
Molten Salts, 3-7 November 2014, Shanghai University, Shanghai, China.
Performance analysis of thermoelectric modules using polyhedron elements; X.N. Meng and R. O. Suzuki : 11th Annual Meeting of Thermoelectric Society ofJapan, 29-30 Sept., 2014, NIMS., Tsukuba, Ibaraki, Japan.
Optimization of Thermoelectric Systems Using Radiative Heat; K. Ito and R. O.
Suzuki : ibid.
Fabrication of micro-porous alloy by calciothermic reduction for electrolytic
capacitor applications ; T. Kikuchi, M. Yoshida, S. Natsui, H. Habazaki and R. O.
Suzuki : The Autumn Meeting of Electrochem. Soc. of Jpn., Sapporo, Japan, Sep.,
2014.
Conversion of CO2 to CO by electrolysis in molten LiCl-Li2CO3; T. Wakamatsu,
F. Matsuura, H. Hada, S. Natsui, T. Kikuchi and R. O. Suzuki : 168th Annual
Meeting of Iron and Steel Institute of Metals (Fall session), 24-26 Sept., 2014,
Nagoya Univ., Nagoya, Aichi, Japan.
CO gas production from CO2 gas by electrolysis in molten salt; F. Matsuura, H.
Hada, T. Wakamatsu, S. Natsui, T. Kikuchi and R. O. Suzuki : ibid.
Reduction of CaTiO3 by molten salt electrolysis; H. Hada, H. Noguchi, S. Natsui,
T. Kikuchi and R. O. Suzuki : ibid.
Characterization of Liquid Trickle Flow in Poor Wettability Packed Bed; S. Natsui,
T. Kikuchi, R. O. Suzuki, T. Kon, S. Ueda and H. Nogami : ibid.
Influence of Wettability on Interparticle Droplet Holdup; T. Kon, S. Natsui, S.

19

Ueda, N. Maruoka and H. Nogami : ibid.
3-dimensional numerical analysis of metal emulsion using multiphase particle
method; H. Takai, S. Natsui, T. Kumagai, T. Kikuchi and R. O. Suzuki : ibid.
Effect of graphite electrodes on the CO2 reduction by calciothermic reduction; R.
Ishida, T. Kikuchi, S. Natsui, N. Sakaguchi and R. O. Suzuki : 155th Annual
Meeting of Japan Institute of Metals (Fall session), Nagoya, Japan, Sep., 2014.
Clarification of the tension instability and dispersion mechanisms of molten metalslag interfaces; S. Natsui, H. Takai, T. Kumagai, T. Kikuchi and R. O. Suzuki :Shigen-Sozai 2014 (Annual Meeting of The Mining and Materials Processing
Institute of Japan), Kumamoto, Japan, Sep. 2014.
3D Numerical Analysis of Gas-Liquid-Liquid Multiphase Flow Using Particle
Method, H. Takai, S. Natsui, Takehiko Kumagai, T. Kikuchi and R. O. Suzuki :ibid
Anodizing of aluminum in etidronic acid - Fabrication of highly ordered porousalumina with large cell diameter; O. Nishinaga, T. Kikuchi, S. Natsui and R. O.
Suzuki : The 130th Annual Meeting of Surf. Finish. Soc. Jpn., Kyoto, Japan, Sep.,
2014.
Fabrication of porous tungsten oxide films and their photocatalytic activities; J.
Kawashima, T. Kikuchi, S. Natsui and R. O. Suzuki : ibid.
Fabrication of anodic porous alumina in ketoglutaric acid solution; D. Nakajima,
T. Kikuchi, S. Natsui and R. O. Suzuki : ibid.
Fabrication of anodic porous alumina via anodizing in cyclic oxocarbon acid; T.
Kikuchi, D. Nakajima, J. Kawashima, S. Natsui and R. O. Suzuki : ibid.
CO2 Decomposition by Electrolysis in CaCl2-CaO Melt; R. O. Suzuki, T.
Uchiyama, T. Wakamatsu, K. Otake, M. Kitamura, S. Natsui, N. Sakaguchi andT. Kikuchi : 65th Annual Meeting of the International Society of Electrochemistry,
31 August - 5 September, 2014 EPFL, Lausanne, Switzerland.
Direct Observation of CO2 Decomposition Behavior by Electro-reduction in LiCl-

20

KCl Eutectic Melt; S. Natsui, M. Kitamura, T. Wakamatsu, T. Kikuchi and R. O.
Suzuki : ibid.
CO2 Decomposition by Electrolysis in Molten LiCl-Li2CO3; T. Wakamatsu, T.
Uchiyama, S. Natsui, T. Kikuchi and R. O. Suzuki : ibid.
Development of oxide and silicide thermoelectric materials and modules; R.
Funahashi, Y. Matsumura, R. O. Suzuki, S. Katsuyama, T. Takeuchi, E. Combeand T. Barbier : 5th International Congress on Ceramics (ICC5), Beijing, 18th
August, 2014.
CO gas formation from CO2 using molten salt electrolysis; F. Matsuura, T.
Wakamatsu, H. Hada, S. Natsui, T. Kikuchi and R. O. Suzuki : Summer session of
FY_2014, Hokkaido committee of both JIM and ISIJ, 28 July, 2014, Hokkaido
Univ., Sapporo, Hokkaido, Japan.
Shape optimization of thermoelectric generator under constant heat flux; K. Ito and
R. O. Suzuki : ibid.
CO2 decomposition by electrolysis in LiCl-Li2CO3 melt using ZrO2 anode; T.
Wakamatsu, T. Uchiyama, S. Natsui, T. Kikuchi and R. O. Suzuki : ibid.
CO2 gas decomposition by low temperature molten chloride electrolysis; H. Hada,
T. Uchiyama, T. Wakamatsu, F. Matsuura, S. Natsui, T. Kikuchi and R. O. Suzuki :ibid.
Effect of electrolyte solution on the growth behavior of anodic oxide films; D.
Nakajima, T. Kikuchi, S. Natsui and R. O. Suzuki : ibid.
Fabrication of tungsten oxide films via anodizing; J. Kawashima, T. Kikuchi, S.
Natsui and R. O. Suzuki : ibid.
Modeling of Gas-Liquid-Liquid Flow using 3-dimensional Multi-phase Particle
Method; H. Takai, S. Natsui, T. Kikuchi and R. O. Suzuki : ibid.
Simulation analysis for thermoelectric elements having the tilted polyhedronshape; X.-N. Meng and R. O. Suzuki : 33rd International Conference on
Thermoelectrics, (ICT2014), July 6-10, 2014, Renaissance Nashville Hotel,

21Nashville, Tennessee, USA.
Dimension of thermoelectric power generation module under constant heat flux;
K. O. Ito and R. O. Suzuki : ibid.
Development of new silicide thermoelectric modules; R. Funahashi, Y. Matsumura,
R. O. Suzuki, S. Katsuyama, T. Takeuchi, E. Combe and T. Barbier : ibid.
Fabrication of Highly Ordered Anodic Porous Alumina by Selenic Acid
Anodizing; O. Nishinaga, T. Kikuchi, S. Natsui and R. O. Suzuki : AST2014, 2ndInternational Symposium on Anodizing Science and Technology, Sapporo, Japan,
June, 2014.
Heat and Mass Transfer Simulation of Low-carbon Blast Furnace using DEMCFD; S. Natsui, T. Kikuchi and R. O. Suzuki : Spring Annual Meeting of The
Society of Powder Technology, Japan, Kyoto, Japan, 29-30 May, 2014.
3-Dimensional Numerical Analysis of Molten Metal-Slag-Gas Multiphase Flow
Using Particle Method; S. Natsui, H. Takai, T. Kikuchi and R. O. Suzuki : Annual
Meeting of The Mining and Materials Processing Institute of Japan, Tokyo, Japan,
26-28 March, 2014.
CO2 decomposition using zirconia and molten salt; R. O. Suzuki, T. Kikuchi, N.
Sakaguchi, M. Ueda, T. Kumagai, S. Natsui, I. Ogino, T. Uchiyama, T. Wakamatsu,
R. Ishida, M. Kitamura, F. Matsuura and H. Hada : 167th Annual Meeting of Iron
and Steel Institute of Metals (Spring session), 21-23 March, 2014, Tokyo Inst. Tech.,Tokyo, Japan.
Numerical Analysis of Metal Emulsion Using 3-dimensional Multiphase Particle
Method; H. Takai, S. Natsui, T. Kumagai, T. Kikuchi and R. O. Suzuki : ibid.
Simulation of Gas-Liquid Dispersion Behavior Using Multiphase Particle Method;
S. Natsui, H. Takai, T. Kumagai, T. Kikuchi and R. O. Suzuki : ibid.
T. Wakamatsu, T. Uchiyama, S. Natsui, T. Kikuchi, R. O. Suzuki, U. Hatanaka and
K. Ohno : 154th annual meeting of Japan Institute of Metals (Spring session), 2123 March 2014, Tokyo Inst. Tech., Tokyo, Japan.

22Effect of iron catalyst on the calciothermic reduction of CO 2 and synthesis of
CNTs; R. Ishida, T. Kikuchi, S. Natsui, N. Sakaguchi and R. O. Suzuki : ibid.
Nanostructure fabrication via selenic acid anodizing; O. Nishinaga, T. Kikuchi,
S. Natsui and R. O. Suzuki : The Winter Joint Meeting of the Hokkaido Branch of
Academic Societies of Chemistry, Sapporo, Japan, Jan., 2014.
Fabrication of anodic porous alumina via anodizing in Meldrum’s acid solution;
A. Sado, T. Kikuchi, S. Natsui and R. O. Suzuki : ibid.
CO gas formation from CO2 gas using molten salt electrolysis; F. Matsuura, T.
Uchiyama, T. Wakamatsu, S. Natsui, T. Kikuchi and R. O. Suzuki : Winter sessionof FY2013, Hokkaido committee of both JIM and ISIJ, 23 -24 Jan., 2014, Hokkaido
Citizens Actives Center, Hokkaido, Japan.
Growth behavior of nanoporous alumina via anodizing in squaric acidT. Yamamoto, T. Kikuchi, S. Natsui and R. O. Suzuki : ibid.

solution;

Fabrication of CNTs via calciothemic reduction of CO2; R. Ishida, T. Kikuchi, S.
Natsui, N. Sakaguchi and R. O. Suzuki : ibid.

Facilities and Capabilities
X-ray diffractmeter: Philips X’Pert Pro. A set for thin film XRD and powder XRD,
and another set for high temperature XRD using Pt heating planer stage or Al2O3
crucible with RF heating.
Oxygen and Nitrogen Analyzer: LECO TC-600. Inert gas extraction with carbon
crucible and infrared absorption method. 5mass%-0.05 mass ppm.
Sulfur and Carbon Analyzer: LECO CS-600. Carbon and nitrogen are converted to
CO and NO gas by burning in O2 gas with RF heating and they are detected by the
infrared absorption method.
CO/CO2 Gas Analyzer IR-400: 4 sets. Yokogawa
Gas Chromatography, Shimazu
NO/SO2 Gas Analyzer IR-400: Yokogawa. In the range of 0.1 vol% and 2 vol%.

23

Constant voltage generators: Takasago Electrics. 4 sets. Max.50V and 20 A.
High voltage amplifier: Takasago Electrics. 100V-8000V.
Thermal Analyzers: SII EXSTAR-6000 TG/DTA. With Pt heater up to 1500C.
Thermal Conductivity Measuring Unit: Kyoto Electrics. Hot disk method at room
temperature.

24

AFFILIATE MEMBERS

AFFILIATE MEMBER
Prof. Dr. Kazuhisa Azumi: Laboratory of Electronic Materials Chemistry
TEL/FAX: +81-11-706-6747
Email: azumi@eng.hokudai.ac.jp

Students
Masaki Aomi, Ali Shaaban, Yusuke Sato, Yuto Nagai, Shohei Yamazoe, Keishi
Inoue, Hiroki Murakoshi, Satoshi Oguma, Takumi Kato, Yuto Yoshikawa

Our group has been investigated various research subjects related to corrosion
engineering, surface finishing of metals, and development of new technologies
of electrochemistry related to energy and environment. Current topics arefollowings:(1) Controlling co-electrodeposition of metals by using a double counterelectrode electrodeposition system.
A double counter electrode electrodeposition system was developed
to enable co-electrodeposition of Al and Zn with a desired composition. Thissystem switches the active counter electrodes of different metals as a metal ion
source to alter the composition of an EMIC-AlCl3-based ionic liquid bath. Using
an integrated counter electrode composed of Al and Zn plates and a thinelectrolyte cell, Al and Zn were co-electrodeposited on a Cu plate substrate by
the galvanostatic pulse method. The effects of electrodeposition current density,
distance between the working and counter electrodes, and electric charge ratioof anodic dissolution on the Al and Zn counter electrodes on the composition of
coatings were examined. Experimental results confirmed that current density
and charge ratio affected the composition of the coatings. On the other hand, thedistance between the counter and the working electrode showed a rather
complicated effect on the coating composition. This was explained by thetransition of the transport mechanism of Zn ions supplied from the Zn counter27

electrode to the working electrode surface via the ionic liquid bath depending on
the distance.

(2) Application of coupling photocurrent method to atmospheric corrosion
A coupling photocurrent method developed in this laboratory
enables in-situ measurement of semiconductor properties corroding in wet anddry corrosion condition. In this method, a couple of specimen of same metal was
irradiated by UV or Vis light emitted from LED pulse modulated and couplingcurrent responding to the light modulation frequency was detected by using a
lock-in amplifier. One of two specimen was corroded by NaCl dispersion to
enable asymmetric corrosion progress on two specimens and thus couplingcurrent was activated from corroding specimen to the other. This method wasapplied to hot-dip Zn-Al alloy coated steel and Cu plate placed in a wet and drychamber. In case of Zn-Al alloy coatings, response of n-type ZnO (EBG = 3.2eV) and p-Si (EBG = 1.1 eV) were observed for UV and Vis light, respectively,changing with corrosion progress. Dependence of coupling photocurrent on bias
between the two electrodes confirmed the n-type or p-type response. Cu sample
also revealed coupling photocurrent to the visible light irradiation due toformation of Cu oxide with p-type semiconductor properties.

(3) Photo-electrochemical investigation of low-Cr alloyed ironCorrosion behavior of iron (99.5%, 4N and 5N) and low-Cr (up to7%) alloyed iron was investigated by measuring the electrochemical
polarization, photocurrent spectra, and impedance spectra in pH 3 phosphate
solution. The samples were also subjected to the outdoor exposure test for aseveral months. In the exposure test, Fe7%Cr showed slightly better corrosion
resistivity than the others. In the laboratory tests, all iron samples and low Cr
alloyed iron samples showed similar n-type semiconductor properties under theanodic polarization condition due to formation of the iron passive films. On theother hand intensity of photocurrent decreased with increase anodic oxidation
time on Fe7%Cr alloy while change in spectra was not clear. Such transition ofphotocurrent response should be related to the compositional changes of the28

passive film under the anodic polarization in the acidic solution such asenrichment of Cr ions and thinning of the passive films.

(5) Electrochemical CO2 reduction in hydrophobic ionic liquid
Electrochemical reduction of CO2 to methane in EMIm-TFSI (1ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide) ionic liquid had
been investigated. EMIm-TFSI was known to absorb CO2 gas and thus
considered as an electrolyte medium for electrochemical CO 2 reduction. Twocompartments electrochemical cell composed of ionic liquid bath with Cu
cathode and KOH aqueous solution bath with Pt anode separated by a proton
conducting membrane was used for efficient reaction. Methane and hydrogengas sensors placed at the gas outlet of the cell confirmed formation of CH 4 andH2 gases under the cathodic polarization of Cu electrode in ionic liquid saturated
with CO2 gas. Currently gas chromatograph is building into to the gas line of thesystem for quantitative analysis to find the optimimul polarization condition.

(6) Corrosion monitoring of Cu foil embedded in swelled bentonite clay
Cu has been considered as a candidate for metal container of highlevel radioactive nuclear waste vitrification produced in nuclear power plants.
The containers are required to separate their contents from human sphere forvery long term as 10000 years. To achieve this, it is planned that the containers
are covered with bentonite clay layer as a mechanical buffer and a transportation
barrier and stored at repository deep underground around 500 m. Corrosion
resistivity of metal container for long period is thus important issue to ensure
the long-term repository of nuclear waste. Metal corrosion may progress in thecondition of high temperature due to residual nuclear fission reaction, contactingwith water passed through bentonite clay containing various ions such ascarbonate, sulfate and chloride, changing oxygen level from atmosphere level toalmost zero level depending on the repository stage and high mechanical stressdue to rock pressure after sealing the repository. To evaluate the actual
corrosion rate of Cu embedded in swelled bentonite clay, an integrated corrosion
monitoring system was built including in-situ measurement of resistometry,29

impedance, corrosion potential and coupling current between two Cu foil
specimens under controlling temperature and oxygen level for long period as afew months. In the test experiments, it was confirmed that the corrosion
behavior of Cu in swelled bentonite clay differed considerably from that in the
aqueous solutions containing similar ions.
(7) Promotion of α-Al2O3 formation on an Ni–Al alloy using a Ni–Fe2O3 nanocomposite seeding layer
Thin seeding layers of Ni and Ni–Fe2O3 composites weresuccessfully formed on an Ni50Al alloy using the pulse electrodeposition
method (PED) from a Watts bath in order to promote α-Al2 O3 formation forimproving the high temperature oxidation resistance of the Ni50Al alloy. The
conditions for the PED and the effects of these seeding layers on Al2O3 scale
formation on the Ni50Al alloy were investigated. The coated samples showed
thicker oxide scales than bare Ni50Al samples in oxidation tests at 1000 °C in
air. At the initial stage of oxidation (1 h), a single layer scale composed ofblade-like crystals of metastable θ-Al2O3 was formed. The oxide scales formedon the PED coated samples had a multilayered structure consisting of an inner
layer of either a mixture of θ- and α-Al2O3 or of single-phase α-Al2O3,
intermediate NiAl2O4 layer and an outer NiO layer. The Ni- seeding layer was
found to delay the phase transformation of θ- to α-Al2O3 to 100 h of oxidation.
Addition of 3.1% Fe 2O3 to the Ni-seeding layer accelerated the transformationof θ- to α-Al2O3 after 9 h of oxidation. Further addition of Fe2O3 nano-powder(5.2%–7.4%) to the Ni-seeding layer successfully suppressed the θ-Al2O3
formation even at 1 h of oxidation.

Presentation
K. Azumi; Development of corrosion monitoring resistometry for field works,
Annual meeting of Japan Society of Corrosion Engineering 2014，Yonago,
Nov. 26-28, 2014.

30

Y. Sato, K. Azumi; An-Zn plating from ionic liquid bath using a double counterelectrodeposition method, The 130th Annual Meeting of Surf. Finish. Soc. Jpn.,
Sept. 22-13, Kyoto university of science, 2014.
H. Murakoshi, K. Azumi, M. Ueda; Optimization of Zn plating on AZ31 alloy
from molten salt bath, ibid.
K. Azumi; In-situ atmospheric corrosion monitoring using resistometry,
EuroCorr2014, Pisa, Italy, Sept. 7-11, 2014.
Y. Sato, K. Azumi; Electrocodeposition of Al-Zn alloy by using double counterelectrodes system, ibid.
K Azumi; Recent progress in electrochemistry using ionic liquid, NTTH
Symposium, Sapporo, Japan, July 21–24, 2014.
N. Murakami; Atmosphere dependence of electric conductivity of polypyrrole,
ibid.
S. Kashima; Fabrication and characteristics of poly (3- octyloxythiophene) thinfilm transistor, ibid.
A. Shaaban, K. Azumi, and S. Hayashi; Effect of nano metal coatings on growth
kinetics of α-Al2O3 formed on Ni-50Al alloy, ISHOC 2014, Hakodate, June 2327, 2014.
A. Shaaban, S. Hayashi, K. Azumi; Effects of nano coatings on hightemperature oxidation kinetics of NiAl Alloy, FCC symposium, Hokkaido
Univ., June 13-14, 2014.
Y. Sato, K. Azumi; Electrocodeposition of Al-Zn layer by using double counterelectrodes method, ibid.
H. Murakoshi, K. Azumi, and M. Ueda; Optimization of electrodeposition Al on
Mg Alloy from the molten salt bath, AST2014，Barato, June 4-6, 2014.
Y. Nagai, K. Azumi; Corrosion monitoring of metals embedded in bentonite
clay, ibid.

31

S. Yamazoe, K. Azumi; In-situ coupling photocurrent method for atmosphericcorrosion", ibid.
Sato and K. Azumi; Electrodeposition of Al-Zn alloy layer by applying double
counter electrodes system, ibid.
A. Shaaban, K. Azumi, S. Hayashi ; Effect of nano metal coatings on growth
kinetics of α-Al2O3 Scale Formed on Ni-50Al Alloy, 9th Intern. Conf.
Microscopy of Oxidation, University of Nottingham, UK, April14-16, 2014.
K. Azumi, Y. Tsugawa ; Application of water absorbing polymer to electrolytic
probe for corrosion monitoring, Annual meeting of Japan Society of Corrosion
Engineering, 2014, Tokyo, May 18-20, 2014.
H. Murakoshi, K. Azumi, M. Ueda ; Optimization of Al deposition on Mg alloy
from molten salt bath, The 129th Annual Meeting of Surf. Finish. Soc. Jpn.,
March 13-14, Tokyo university of science, 2014.
Y. Sato, K. Azumi; Al-Zn alloy plating by using a double counterelectrodeposition method , 81th Annual meeting of Japan Society ofElectrochemistry, Kansai university, March 29-31, 2014.
S. Yamazoe, K. Azumi; Development of in-situ coupling photocurrent method
for atmospheric corrosion, ibid.
K. Inoue, K. Azumi, S. Kajiyama; Comparison of electrochemical properties ofiron with different purity, ibid.
K. Azumi; Development of a new measurement method of atmosphericcorrosion, NIMS-HU seminar，NIMS, Feb. 21, 2014.
K. Inoue, K. Azumi; Photoelectrochemical response of passive film formed onhigh purity iron, Winter Joint Meeting of the Hokkaido Branch of the Chemistry
Related Societies, Sapporo, Jan. 28-29, 2014.
K. Suetake, K. Azumi; Efficient electrochemical CO2 reduction using ionicliquid, ibid.

32

H. Murakoshi, K. Azumi; Optimization of Al plating on Mg alloys from molten
salt bath, ibid.

33

AFFILIATE MEMBER
Assoc. Prof. Dr. Koji Fushimi
Tel./FAX: +81-11-706-6737
E-mail: kfushimi@eng.hokudai.ac.jp

Students
J-.S. Lee, Y. Takabatake, H. Ikeyama, M. Jin, K. Yanagisawa, Y. Yamamoto, M.
Goto

The research activities of the laboratory are directed to the materials surface scienceand engineering. We are interested in the micro-electrochemistry for a better
understanding of the interfacial phenomena of metal and semiconductor electrodes
in relation to electrochemical devices, corrosion, passivation, and surface finishing.
Current topics on research are as follows:(1) Grain-dependent Passive State of Iron Single Grains in Sulfuric Acid
Passivation of single grains on a polycrystalline pure iron was investigatedin sulfuric acid with a micro-capillary-cell. Passivation behavior of the iron single
grains under potentiostatic polarization depended on the crystallographic
orientation of a substrate iron surface. Electrochemical impedance spectroscopy
and cathodic reduction of the surface passivated on single grains revealed that the
charge transfer resistance and the thickness of passive films depended on theorientation and that the thicker oxide film exhibited the smaller resistivity. XPS
analysis evaluated that the composition of the film varied among the surface
orientations. It was suggested that the structure of the passive film depended on theorientation of the iron substrate due to different surface energy and work function
on each crystallographic orientation of bcc iron.
(2) Corrosion Behavior of Dual-Phase Carbon Steel and Super Duplex Stainless
Steel

34

Corrosion behavior of high-purity dual-phase carbon steel composed ofonly ferrite and martensite phases in 0.1 M sulfuric acid was investigated by both
macro- and micro-electrochemical methods. The dual-phase steel corrodes
non-uniformly due to galvanic coupling between its microstructures as well as
self-corrosion of each phase. Hydrogen evolution reaction on galvanic-coupledmartensite accelerates iron dissolution reaction of ferrite, though the corrosion
rate of martensite was three-times larger than that of ferrite due to the selfcorrosion in the acid. Totally, ferrite phases corrode selectively and the degreeof selective corrosion was about two-times larger than martensite phases.
Corrosion behavior of super duplex stainless steel (SDSS) in acidic chloride
solution was also investigated electrochemically. Potentiostatic polarizations of
SDSS at -0.377 and -0.447 VSHE resulted in selective dissolution of gamma- andalpha-phases, respectively, and were utilized for fabricating single-phaseelectrodes. Potentiodynamic polarization curve of SDSS could be calculated fromthose of single-phase electrodes. The higher corrosion current density and lessnoble corrosion potential of alpha-phase characterized by galvanic connection withgamma-phase indicated that alpha- and gamma-phases were functioned as theanode and the cathode, respectively, in the corrosion of SDSS.
(3) In-situ observation of passive surface by using an ellipso-microscope andelectrochemical impedance spectroscopy during UV-light irradiation
Photo-corrosion of an anodized titanium surface in 0.05 mol dm−3 sulfuric
acid solution was investigated by using an in situ electrochemical ellipsomicroscope. Irradiation of UV-light on an anodized surface, which showed apatch-like bright image on an ellipso-microscopic view due to non-uniform
growth of the oxide film, under potentiostatic polarization allowed the flow ofa photo-induced anodic current and changed the brightness and patch pattern in
the image. This indicates that the irradiation promotes photo- electrochemical
reaction, resulting in a change in the thickness and/or structure of the oxide filmon the surface. The film change was dependent not only on power density of theirradiation light but also on applied potential during the irradiation andcrystallographic orientation of the substrate. Pitting initiation duringpotentiodynamic polarization in the acid with bromide ions was also

35monitored using the ellipso-microscope. The irradiation resulted in pitting
initiation at lower potentials than those in a non-irradiated condition.
(4) Fabrication of Multichannel Microelectrode-array and Its Application
Scanning probe technique such as an SECM enables to visualize theelectrochemical activity on a specimen electrode. However, it is not suitable topursuit the relatively rapid reaction of the electrode such as an initiation of pitting
corrosion. In order to overcome this problem, a microelectrode-array has been
fabricated by MEMS technologies in collaboration with Nanotechnology Platform,
Waseda University. Simultaneously, a numerical calculation of diffusion problem
on the microelectrode array has been conducted. 10x10- channels array structurewith a microelectrode diameter of 10 µm successfully showed limiting currents
flowing through 100 microelectrodes independently. Interference effect between
electrodes in the array was also simulated. These results have been used to redesign the array.
(5) Exploring New SECM Redox Mediator for Corrosive Surface
SECM is an effective tool for investigating the corrosive interface.
Conventionally, it has been used to image passive metal surface by combination ofredox mediator of ferro- or ferri-cyanide ions. In order to extend the application of
SECM measurement in corrosion research, new method and new mediator are
explored. One of candidates for new redox mediator is ferrocenemethanol. DFT offerrocenemethanol as well as other mediator molecules was carried out andrevealed the dependence of the redox potential on LUMO state of the molecule.
Though ferrocenemethanol has a similar redox potential with ferro-/ferri-cyanide
ions, ferrocenemethanol shows a lateral resolution better than ferrocyanide ions
during SECM imaging of passive surface on dual phase carbon steel.
(6) Convection-dependent Hydrogen Permeation into a Carbon Steel Sheet
In order to avoid hydrogen embrittlement of carbon steel sheet, basic research
for mechanism and kinetics of hydrogen penetration is necessary. The DevanathanStachurski double electrochemical cell for measurement of hydrogen-permeation
into a steel sheet was extended to an electrolyte-flowing design. Increase in flowrate of the entry cell induces increase in hydrogen- evolution current at the entryelectrode but decrease in hydrogen-permeation36

current at the hydrogen-exit electrode. Hydrogen-permeation is actualized by asinusoidal perturbation of the entry-flow rate. The hydrogen-permeation response,
i.e., phase shift of the detection current from the evolution current, wasproportional to the square root of flow rate frequency and was dependent on sheet
thickness. The sinusoidal perturbation of entry-flow rate is a new factor
influencing hydrogen-permeation into the sheet.
Other Activities
In June, Dr. Koji Fushimi, Mr. Jun-Seob Lee, and Mr. Yu Takabatake attended to
2nd International Symposium on Anodizing Science and Technology (AST2014)
and presented three papers. Mr, J.-S. Lee and Mr. Y. Takabatake also attended to
The 3rd Frontier Chemistry Center International Symposium “Challenge at the
Frontier of Chemical Sciences” and presented two papers. Mr. Y. Takabatake won
FCC Poster Award. In August, Dr. K. Fushimi, Mr. Kei Yanagisawa, and Mr. Yudai
Yamamoto attended to 65th ISE Annual Meeting, Lausanne, Switzerland andpresented three papers. In September, Dr. K. Fushimi, Mr. J.-S. Lee, and Mr.
Y. Takabatake attended to Eurocorr2014, Pisa, Italy and presented three papers. In
November, Dr. K. Fushimi and Mr. J.-S. Lee attended to 19th International
Corrosion Congress, Jeju, Korea and presented a keynote lecture entitled “Anodic
Dissolution Sequence of Super Duplex Stainless Steel in an Acidic Chloride
Solution” and a paper.

Presentations
K. Fushimi, K. Kurauchi, T. Nakanishi, Y. Hasegawa, M. Ueda, “Ellipsomicroscopic Imaging of Anodized Titanium Surface under UV-light Irradiation”,
2nd International Symposium on Anodizing Science and Technology (AST2014),
Jun. 4-6, Sapporo, Japan (Oral presentation).
Y. Takabatake, K. Fushimi, T. Nakanishi, Y. Hasegawa: “Anodic Oxide Film
Formed on Iron Dependinh on Crystallographic Orientation”, 2nd International
Symposium on Anodizing Science and Technology (AST2014), Jun. 4 -6,
Sapporo, Japan (Poster).
J.-S. Lee, K. Fushimi, T. Nakanishi, Y. Hasegawa: “Generation of Sulfide Ions37

from Ag-Microelectrode on Iron Electrode”, 2nd International Symposium on
Anodizing Science and Technology (AST2014), Jun. 4 -6, Sapporo, Japan(Poster).
J.-S. Lee, K. Fushimi, T. Nakanishi, Y. Hasegawa: "Reduction of Ag2Smicroelectrodes as Sulfide Ion Generator ", The 3rd Frontier Chemistry Center
International Symposium “Challenge at the Frontier of Chemical Sciences”, Jun.
13-14, Sapporo, Japan (Poster).
Y. Takabatake, K. Fushimi, T. Nakanishi, Y. Hasegawa: "Effect of Metallographic
Structure on Electrochemical Oxidation of Pure Iron", The 3rd Frontier ChemistryCenter International Symposium “Challenge at the Frontier of Chemical Sciences”,
Jun. 13-14, Sapporo, Japan (Poster).
K. Yanagisawa, K. Fushimi, T. Nakanishi, Y. Hasegawa, T. Kawano, M. Kimura,“Corrosion of dual-phase carbon steel in 0.1 mol dm-3 sulphuric acid aqueous
solution”, 65th ISE Annual Meeting, Aug. 31-Sep. 5, Lausanne, Switzerland(Poster).
Y. Yamamoto, K. Fushimi, T. Nakanishi, Y. Hasegawa, M. Saito, T. Homma,“Redox reaction current on multi-microdisc electrode”, 65th ISE Annual Meeting,
Aug. 31-Sep. 5, Lausanne, Switzerland (Poster).
Y. Takabatake, K. Fushimi, T. Nakanishi, Y. Hasegawa, “Micro-electrochemical
reactivity of iron single crystal grain during anodic polarisation in 0.05 mol dm-3
sulphuric acid aqueous solution”, 65th ISE Annual Meeting, Aug. 31 -Sep. 5,
Lausanne, Switzerland (Oral presentation).
K. Fushimi, K. Kurauchi, T. Nakanishi, Y. Hasegawa, M. Ueda, T. Ohtsuka; “Nonuniformity of Anodized Titanium Surface under UV-light Irradiation Observed by
Ellipso-microscopy, Eurocorr 2014, Sep. 8-12, Pisa, Italy (Oral presentation).
Y. Takabatake, K. Fushimi, T. Nakanishi, Y. Hasegawa; “Grain-dependency of
passive oxide film formed on iron in sulphuric acid”, Eurocorr 2014, Pisa, Italy,
Sep. 8-12, Pisa, Italy (Oral presentation).

38

J.-S. Lee, K. Fushimi, T. Nakanishi, Y. Hasegawa; “Development of a Liquidphase Sulfide Ion Gun for Localized Sulfidation of Metal Surfaces”, Eurocorr 2014,
Sep. 8-12, Pisa, Italy (Oral presentation).
K. Fushimi, K. Kurauchi, T. Nakanishi, Y. Hasegawa, M. Ueda, T. Ohtsuka;“Ellipso-microscopic Observation of Titanium Surface under UV-light
Irradiation”, 19th International Corrosion Congress, Nov. 2-6, Jeju, Korea (Oralpresentation).
J.-S. Lee, K. Fushimi, T. Nakanishi, Y. Hasegawa, Y.-S. Park; “Anodic Dissolution
Sequence of Super Duplex Stainless Steel in an Acidic Chloride Solution”, 19thInternational Corrosion Congress, Nov. 2-6, Jeju, Korea (Keynote lecture).

39

AFFILIATE MEMBER
Assoc. Prof. Dr. M. Sakairi
Tel.:+81-11-706-7111, Fax.:+81-11-706-7881
E-mail: msakairi@eng.hokudai.ac.jp

Students
T. Sasaki, T. Yamaguchi, K. Igarashi, H. Mizukami, R. Sakaki, F. Nishino, L.
Rao, and R. Itzinger

Mr. Lalith Rao, School of Mechanical Sciences, Indian Institute ofTechnology Bhubaneswar, India, joined our group as internship student form 16th
May 2014 to 16th July 2014. Ms. Regina Itzinger, Johannes Kepler University Linz,
Austria, joined our group as internship student form 14th July 2014 to 5th
September 2014.
Research work of our group directs toward (1) effect of metal cations on
passive film structure of aluminum alloys in model tap water, (2) effect ofCH3COONa concentration on oxide film composition and corrosion behavior of
13 % Cr stainless steel in model oil and gas environments, (3) Effect of surface
condition on hydrogen permeation behavior of zinc coated steels during cyclic wet
and dry corrosion (4) Formation of layer structured porous type anodic alumina
locally by solution flow type micro-droplet cell, (5) effect of water layer thickness
on oxygen reduction reaction on zinc coated steels, 6) formation of multi layer
structure of Cu-Ni with nono-size thickness and its property, and 7)Field exposer
test in cold and heavy snow district.

Current topics on research are in the following:(1) Effect of metal cations on passive film structure of aluminum alloys in model
tap water
It has been reported that the corrosion rate of aluminum alloy in model tap
water is affected by kind of metal cation in the meda, and the effect can be40

explained by metal cation hardness which based on the hard and soft acid and base,
HSAB, concept. It is, however, not clear the influence of substrate on the changeof passive film structure. The effects of metal cations (Na, Mn and Zn) on thepassive film structure of two types of aluminum alloys (A3003 and A5052) were
examined by immersion test, potentiodynamic polarization and electrochemical
impedance method. Form immersion tests, rest potential tends to raise the metal
cation hardness, and its of A3003 was about 0.3 V larger than that of A5052. The
current density of both alloys were decreased with increasing of metal cation
hardness. From the electrochemical impedance observation, film resistance on
A3003 is generally larger than that of A5052.
(2) Effect of CH3COONa concentration on oxide film composition and corrosion
behavior of 13 % Cr stainless steel in model oil and gas environments
An acetic acid is the most common organic acid in oil and gas environments,
therefore, acetate ions sometimes used in simulated oil and gas environments.
However, the role of acetic ions in corrosion behavior and surface film structure.
In this year, the effect of CH3COONa addition, temperature and immersion timeon surface film thickness was examined. Addition of CH3COONa and longer
immersion time lead to small hole formation and surface color change. From XPS
analysis results, even in high concentration of CH3COONa and high temperature,surface film thickness less than 5 nm. The film thickness, however, is affected byimmersion condition. Permeated hydrogen formed during corrosion detected by
micro electrochemical technique and Laser irradiation(3) Effect of surface condition on hydrogen permeation behavior of zinc coatedsteels during cyclic wet and dry corrosion
The wet and dry corrosion test with constant dew point test was applied toinvestigate the effects of composition and corrosion products on the hydrogen
permeation behavior of Zn and Zn alloy coated steels, and uncoated steels during
wet and dry corrosion tests. Independent of the specimen composition and the areaof the formed scratches, the hydrogen permeation current and the corrosion
products were observed. The hydrogen permeation current of the steels with theformed scratches decreased with number of cycles of the wet and dry tests. Except
in the first cycle there were no significant changes in the current with cycle

41

number on steels without formed scratches. It was suggests that the composition,scratch, and corrosion products play an important role in the hydrogen permeation
behavior during wet and dry corrosion.
An area-selective technique for electrochemical hydrogen detection with laser local
activation (focused pulse YAG laser irradiation) was developed, and this technique
was applied to measure hydrogen permeation behavior of iron at selected areas.
(4) Formation of layer structured porous type anodic alumina locally by solution
flow type micro-droplet cell
A solution flow-type micro droplet cell with co-axial dual capillary tubes(Sf-MDC) was applied to form porous type anodic alumina film with layered
structure at selected areas. The anodizing process with different repetition
numbers, yielding different oxide layer numbers was performed with the Sf-MDC.
The fine structure between the layers and its formation mechanism have not beenclarified. The purpose of this year is to clarify the fine structure between the layersof formed porous type anodic alumina films, and also determine the formation
mechanism of the layered structure in the formed films. The investigation of crosssections of the formed oxide showed that the pore diameter widened at theboundary between layers. From a simulated anodizing process with the Sf-MDC,
the reason for this modification of the pores was suggested to be intermittent
anodizing with processes of drying up of the solution of the pores and widening
at the bottom of the pores.
(5) Effect of water layer thickness on oxygen reduction reaction on zinc coatedsteels
It is well known that thickness of water layer plays an important role incathodic reaction of atmospheric corrosion. However, the relationship between
water layer thickness and oxygen limiting current is not clear. In this study, microelectrode technique was applied to investigate oxygen limiting current change withwater layer thickness on zinc coated steels. In the thickness range form 0.2 mm to
1mm, the oxygen limiting current increase with decreasing water layer thickness
that expect from oxygen diffusion.

426) Multi layer structured of Cu-Ni with nono-size thickness film formation andits property
DC electro-deposition Cu-Ni nano thickness multi layer formation machine
was developed. Using Ti as substrate, makes it possible to peal off the formed CuNi film easily. The layer structure was observed by FIB-SEM and layercomposition by RBS. From simulation of RBS results, Cu and Ni layered structure
was detected, however it become unclear with increasing each layer thickness. The
tensile tests results showed strength of the formed Cu-Ni films were almost same
strength as same thickness of Cu or Ni. It was success fully recorded the crack
propagation under optical microscope.
7) Field exposer test in cold and heavy snow district
The filed exposer test for corrosion of steels in cold and heavy snow district as
Sapporo and Akkeshi in Hokkaido is carrying out in this year. This exposer test isa joint research work of e-Asia corrosion mapping project and, NIMS. A one year
exposure tests sample was finished and new exposure samples of each steels wasset.
Other activities
In February, Assoc. Prof. Sakairi attended 1st international conference on
structural integrity (ICONS-2014) at Kalpakkam India, and presented papers
entitled "Electrochemical noise evaluation of metal cation effects on galvanic
corrosion of aluminum alloys in low concentration of chloride ion containing
solutions".
In June, Assoc. Prof. Sakairi and Mr. Sasaki attended 2nd International
symposium on anodizing surface and technology, AST2014 at Sapporo, Japan, andpresented a paper entitled "Electrochemical noise evaluation of metal cation effects
on galvanic corrosion of aluminum in model tap waters" and "Analysis of passive
film structure formed on A3003 in sulfate solutions".
In September Assoc. Prof. Sakairi and Mr. Sasaki attended AGH-HU joint
symposium at Krakow, Poland, and present papers entitled "Pulsed Laser andmicro-electrochemical techniques applied for detection of permeated hydrogen
during wet/dry corrosion" and "XPS analysis of surface films formed on aluminumalloys in sulfate solutions".

43

In September, 65th ISE annual meeting at Lausanne, present a poster entitled"Area selective Porous type Aluminum Anodic Oxide Film Formation by Solution
flow type Micro-droplet Cell".
In September, Assoc. Prof. Sakairi attended EUROCORR2014 at Pisa Italy, andpresented a paper entitled "Electrochemical noise analysis on modified 13%Cr
stainless steels in sour environments under stress".
In October, Assoc. Prof. Sakairi attended the seventh international symposium on
marine corrosion and control, Nanjing, China, and presented a paper entitled"Metal cation effects on galvanic corrosion behavior of A2024 aluminum alloy
with electrochemical noise."
In November, Assoc. Prof. Sakairi attended 16th international corrosion congress,
16th ICC, at JeJu, Korea, and presented a paper entitled "Improvement of corrosion
resistance of aluminum with wettability controlled porous oxide films."
In November-December, Assoc. Prof. Sakairi attended Forschung und Studim inJapan at Universität Wien, Aula Am Campus, Viena, Austria and Hokkaido
University–University of Bremen Inter-University Exchange Seminar at Bremen,
Germany, and during this trip he and Prof. Nawa also visited Prof. A. Hassel,
Johannes Kepler University Linz and discuss about future corroboration.

Presentations
Analysis of passive films formed on A3003 in diluted sulfates solutions by XPS,
R. Sasakai, M. Sakairi, and Y. Kaneko, The Winter Joint Meeting of The Hokkaido
Secs. of Jpn. Inst. Metals and ISIJ, Sapporo, January, 2014.
Anodic oxide film growth rate change with repetition number during Sf-MDC
anodizing, T. Yamaguchi and M. Sakairi, The Hokkaido Secs. of Chem. Soc. Jpn.
And Jpn. Soc. Anal. Chem. Sapporo, January, 2014.
Evaluation of metal cation effects on galvanic corrosion of aluminum alloys in low
chloride ion containing solutions with electrochemical noise, M. Sakairi, K. Otani,
and R. Sasaki, ICONS2014, Kalpakkam, Indea, February, 2014.
Formation of porous alumina film locally by Sf-MDC, M. Sakairi and44

T.

Yamaguhchi, The 129th meeting of Surf. Fin. Soc. JPN, Tokyo, March, 2014.
Formation of Cu-Ni multi layer by electro-deposition and investigation of theproperty, M. Sakairi, S. Miura, K. Ohkubo and S. Nagata, The 81th spring meetingof Electrochemistry Japan, Osaka, March, 2014.
Influence of metal cation on corrosion behavior of Al alloy in fresh waters, M.
Sakairi, K. Otani, R. Sasaki and A. Kaneko, The Hokkaido Sec. of Light metal soc.,
Sapporo, April, 2014.
Detection of permeated hydrogen during wet/dry corrosion at laser machined
scratch formed on coated steels, M. Sakairi, S. Takagi and K. Igarashi, Zairyo-toKankyo 2014, Tokyo, May, 2014.
Investigation of passive film formed on Al alloy in fresh water containing metal
cations, R. Sasaki, M. Sakairi, and A. Kaneko, ibid.
Electrochemical noise evaluation of metal cation effects on galvanic corrosion ofaluminum in model tap waters, M. Sakairi, K. Otani, R. Sasaki, and A. Kaneko,
ASST2014, Sapporo, June, 2014.
Analysis of passive film structure formed on A3003 in sulfate solutions, R. Sasaki,
M. Sakairi, and A. Kaneko, ibid.
Analysis of passive film formed on 13Cr steel in acid NaCl solutions, Summer Joint
Meeting The Hokkaido Secs. of Chem. Soc. Jpn. And Jpn. Soc. Anal. Chem.,
Tomakomai, July, 2014.
Effect of alloying elements on passive film structure formed on Al alloys, R. Sasaki,
M. Sakairi, and A. Kaneko, The Summer Joint Meeting of The Hokkaido Secs. of
Jpn. Inst. Metals and ISIJ, Sapporo, July, 2014.
Hydrogen permeation behavior at scratch formed on Zn coated steel during wet/dry
corrosion, K. Igarashi, M. Sakairi, and S. Takagi, ibid.
Exploring the Use of High Cr Oxide Dispersion Strengthened Steels Cladding inFuel Reprocessing Environment, S. Ningshena, M. Sakairi, K. Sukuzi, S. Ukai, andU. Kamachi Mudali, International conference on Advancements in Materials,

45

Health and Safety towards Sustainable Energy & Environment (MHS-2014),
Chennai, India, August, 2014.
Pulsed Laser and micro-electrochemical techniques applied for detection of
permeated hydrogen during wet/dry corrosion, M. Sakairi and S. Takagi, AGHHU joint symposium at Krakow, Poland, September, 2014.
XPS analysis of surface films formed on aluminum alloys in sulfate solutions, R.
Sasaki, M. Sakairi, and A. Kaneko, ibid.
Area selective Porous type Aluminum Anodic Oxide Film Formation by Solution
flow type Micro-droplet Cell, M. Sakairi, T. Yamaguchi, and K. Fushimi, Lausanne,
Switzerland, September, 2014.
Electrochemical noise analysis on modified 13%Cr stainless steels in sour
environments under stress, M. Sakairi, J. Tatehara and Y. Mizukami, and H.
Hashizume, Eurocorr2014, Pisa, Italy, September, 2014.
Microstructural Characterization and Corrosion Resistance of Mechanically
Alloyed Oxide dispersion strengthened steels, S.Ningshen, M. Sakairi, K. Suzuki,
S. Ukai, and U. Kamachi Mudali, DAE-BRNS National Conference on Current
Trends in Advanced Materials (CTMat-2014), Kolkata, India, September, 2014.
Local porous anodic alumina film formation by Sf-MDC, M. Sakairi and T.
Yamaguchi, Autumn meeting of Jpn. Inst. Metals, Nagoya, September, 2014.
Effect of cations on electrochemical noise obtained during galvanic corrosion of
Al in model tap water, M. Sakairi, K. Otani, R. Sasaki, and A. Kaneko, Autumn
meeting of Electrochemical Society Japan, Sapporo, September, 2014.
Corrosion behavior of Al alloys in model tap water, R. Sasaki, M. Sakairi, A.
Kaneko, Corrosion dream2014, Osaka, October, 2014.
Metal cation effects on galvanic corrosion behavior of A2024 aluminum alloy withelectrochemical noise, M. Sakairi, A. Kaneko, and R. Sasaki, The seventhinternational symposium on marine corrosion and control, Nanjin, China, October,
2014.

46

Formation of hydrophobic surface on aluminum by anodizing and drying treatment,
M. Sakairi and V. Goyal, The 127th Autumn meeting of Jpn. Light Metal Soc.,
Tokyo, November, 2014.
Relationship passive film structure and corrosion behavior of 13Cr stainless steelsin acid NaCl solutions, H. Mizukami, M. Sakairi, s. Hashizume, and T. Taniguchi,
The 61st discussion meeting of Zairyo-to-Kankyo, Yonago, November, 2014.
Effect of metal cation in model tap water on electrochemical behavior of Al alloys,
ibid.
Improvement of corrosion resistance of aluminum with wettability controlled
porous oxide films, M. Sakairi and V. Goyal, 16th International corrosion congress,
Jeju, Korea, November, 201

47

ABSTRACT of PUBLICATIONSElectrorefining of Sodium in SodiumBis(trifluoromethane)sulfonylimide andTetrabutylammonium Bis(trifluoromethane)sulfonylimide
Mixture Ionic Liquids for Metallic Sodium Recycling
M. Ueda, R. Inaba, H. Matsushima and T. Ohtsuka
ECS Electrochemistry Letters, 4, E1-E3 (2014)
To develop an electrorefining process for sodium to enable
recycling of used sodium-sulfur batteries, a non-aqueous electrolyte withlow melting point was investigated. A mixed ionic liquid of NaTFSI(sodium bis (trifluoromethane) sulfonylimide) - TBATFSI(tetrabutylammonium bis (trifluoromethane) sulfonylimide) was selected
for the electrolyte. From AC impedance measurements, a maximum ionic
conductivity of 16 mS cm-1 was established of 20 mol% NaTFSITBATFSI concentration at 433 K. Electrorefining for 20 hours was carriedout with a stable voltage under constant current electrolysis. Liquid puresodium was electrodeposited by the constant current electrolysis. The
calcium content in the sodium cathode was decreased from 250 to 52 ppm
by the electrorefining.

51

Observation of Three-Phase Interface during Hydrogen
Electrode Reactions in Unitized Regenerative Fuel Cell
W. Majima, H. Matsushima, Y. Fukunaka and M. Ueda
Journal of The Electrochemical Society, 161, F1002-F1005 (2014)
The dynamic behavior of the meniscus of a potassium hydroxide andsulfuric acid droplet on a platinum electrode was studied using a charge-coupleddevice (CCD) camera and confocal laser microscopy. The three-phase interface
was investigated during the hydrogen oxidation reaction (HOR) and the hydrogen
evolution reaction (HER). Contact angle measurements revealed a spreadinginterface during the HER whereas the droplet shape remained unchanged during
the HOR for both droplets. The overhead view revealed the formation of many fine
droplets near the meniscus boundary during the HOR in the alkaline electrolyte,
which agrees with previous results for the oxygen reduction reaction (ORR). The
correlation of these observations with electrochemical data and differences in the
results between the HOR and the HER suggest that the motion of the meniscus was
induced by local pH and temperature gradients, presumably caused by a nonuniform reaction because of the limitations of the dissolved gas.

52

Output Characteristics of a Circular Cone Type Graphite
Cathode for Al-Cl2 Fuel Cells in AlCl3-EMIC Ionic Liquid
J. Nunomura, M. Ueda, and T. Ohtsuka
Z. Phys. Chem, 228, 685-689(2014)
To improve the reduction efficiency of chlorine electrodes inaluminum-chlorine cells, this reports a circular cone type graphite cathode, with anelectrochemical cell consisting of an aluminum anode and the graphite cathodeevaluated in EMIC-AlCl3 ionic liquid. The current density in the circular cone type
cathodes with different cone angles exhibited a maximum value at 40○, and thecurrent density at cell voltage of 0.5 V was about 25 mA cm–2. This value is about
80% larger than that of a cylindrical type graphite cathode. In a circular cone type
cathode with a 40 ○ angle, the maximum power density recorded was 15.3 mW cm–
2.

53

Improvement of Protective Polypyrrole Film forCorrosion of Zinc-Coated AZ91D AlloyNan Sheng, YanHua Lei, Mikito Ueda, and Toshiaki Ohtsuka
Progress in Organic coating, 77, 1724-1734 (2014)
To improve the protection against the corrosion of AZ91D magnesium
alloy provided by conducting polypyrrole (PPy) films, optimization of theelectrochemical synthesis of the PPy film was investigated. The bi-layered PPy
film was prepared under constant current control, first in a sodium tartrate solution
containing molybdate and second in a sodium dodecylsulfate (DS) solution (after
the AZ91D alloy was covered by zinc electroplating). Corrosion testing of the zinccoated AZ91D alloy covered with the PPy film was performed in 3.5% NaClsolution. The more protective PPy film doped with tartrate ions (PPy-Tart film) was
formed by the lower current density (CD). Doping of molybdate ions (MoO42−)
into the PPy-Tart film significantly improved its corrosion protection properties.
When the PPy-Tart-MoO4 layer was covered by an outer PPy layer doped with DS
ions, the corrosion protection was further improved. The imposition of ultrasonicwaves during the electropolymerization of the inner PPy-Tart-MoO4 layer was
effective in the improvement of corrosion protection. The bi-layered PPy-TartMoO4/PPy-DS film prepared under ultrasonic irradiation maintained the zinccoated AZ91D alloy in the passive state during the corrosion test in NaCl solution
for 221 h, during which no corrosion products appeared.

54

Influence of pH on the Synthesis and Properties of
Polypyrrole on Copper from Phytic Acid Solution forCorrosion Protection
Y. Lei, N. Sheng, A. Hyono, M. Ueda, T. Ohtsuka
Progress in Organic Coatings, 77, 774-784 (2014)
Polypyrrole (PPy) films were deposited on copper from “green”
inhibitor of phytic acid solution for corrosion protection of copper. The corrosion
protection property of the PPy layer was studied by an immersion test in a NaClaqueous solution. The polymerization process of PPy on copper changed with the
pH values of phytic acid solution and current density applied. When one oxidized
bare copper in phytic acid solution at various pHs containing pyrrole monomer, athin layer consisting of complex compound of Cu-phytate was firstly formed,
followed by the formation of the PPy layer doped with phytate anion on thecomplex compound layer. The complex compound layer passivated the copper
surface and its thickness increased with the lower pH value of the solution and thelower current density applied. It was found that the PPy coating prepared in thephytic acid solution at pH 4 exhibit the most protective property against copper
corrosion.

55

Effect of Benzotriazole(BTA) Addition on Polypyrrole
Film Formation on Copper and Its Corrosion Protection
Y. Lei, N. Sheng, A. Hyono, M. Ueda, T. Ohtsuka
Progress in Organic Coatings, 77, 339-346 (2014)
Benzotriazole (BTA) was added in a conducting Polypyrrole (PPy) film
prepared on copper in oxalic acid aqueous solution containing pyrrole monomer toimprove corrosion protection by the PPy film and reduce copper corrosion. When
BTA was added in the preparation solution, the copper surface was covered by a
BTA–Cu complex layer before the anodic polymerization of PPy was started. On
the copper surface with the BTA layer, the initial dissolution of copper was
inhibited and the PPy polymerization-deposition was started immediately after theanodic current was imposed. The PPy film thus formed was doped with oxalic ionsand ionized BTA and was homogeneous in thickness and strongly adhesive. The
PPy film containing BTA protected the copper from corrosion in 3.5 wt.% NaClsolution. In 400 h of immersion, copper dissolution was inhibited with 80%
protection efficiency relative to that of bare copper.

56

Gas Sensing Properties of the Nanostructured Anodic
Zr–W Oxide Film
R. M. Vázquez, A. Mozalev, R. Calavia, F. Gispert-Guirado, X. Vilanova,
H. Habazaki and E. Llobet
Sensors and Actuators B: Chemical, 204, 588-595 (2014)
The sensing properties of nanostructured Zr–W mixed oxide film havebeen investigated. The film was prepared via anodizing a sputter-deposited Zr–W
alloy layer through nanopores in an anodic alumina layer superimposed on thealloy. The morphology, structure and chemical composition of the film were
examined by SEM and XRD. The film consists of an array of self-ordered
nanocolumns protruding from a continuous thin oxide layer. The initiallyamorphous film material crystallizes to monoclinic WO3 and orthorhombic ZrO2
due to a high temperature annealing in air. A sensor employing the ZrO 2–WO3oxide film as active layer was fabricated and used for detecting various
concentrations (1–1000 ppm) of H2, CO, C2H5OH and NO2 at temperatures up to
300 °C. In hydrogen detection experiments, the sensor was very fast, with a
response time of 19 s, and highly sensitive to hydrogen, with a response value ofup to 50, while showing incomparably weaker and slower responses to carbon
monoxide, ethanol and nitrogen dioxide. The features of the films revealed to dateare of importance for improving the chemical, structural and exploitation stabilityof nanostructured tungsten-oxide-based films and their selectivity in hydrogen gas
detection.

57

Morphological Control of Anodic Crystalline TiO2
Nanochannel Films for Use in Size-selective
Photocatalytic Decomposition of Organic Molecules
E. Tsuji, Y. Taguchi, Y. Aoki, T. Hashimoto, P. Skeldon, G. E. Thompson and
H. Habazaki
Applied Surface Science, 301, 500-507 (2014)
We report the size-selective photocatalytic decomposition of organic
molecules using crystalline anodic TiO2 nanochannel films as the photocatalyst.
The porous TiO2 films were formed by anodizing titanium at 20 V in glycerol
electrolyte containing various amounts of K3PO4, K2HPO4, and KH2PO4 at 433K.
Regardless of the electrolyte composition, the as-formed TiO2 films had acrystalline anatase structure. The basicity of the electrolyte markedly influenced
the morphology of the TiO2 nanochannel films; more regular nanochannels
developed with increasing basicity of the electrolyte. Because the diameter of thenanochannels in the films formed in a basic electrolyte was as small as similar to
10 nm, the anodic TiO2 nanochannel films with a thickness of 5 mu m revealed aselective photocatalytic decomposition of methylene blue (MB) in a mixture of MB
and direct red 80 (DR) kept under UV irradiation. The importance of the diameterof the nanochannels and their uniformity for size-selective decomposition oforganic molecules were investigated.

58

In Situ X-Ray Absorption Spectroscopy Study of Sn
Underpotential Deposition on Ni from Perchloric Acid
M. Seo, H. Habazaki, M. Inaba, M. Yokomizo, T. Wakabayashi and T.
Nakayama
Journal of the Electrochemical Society, 161, H195-H202 (2014)
In situ X-ray absorption spectroscopy (XAS) was applied to investigate
the Sn underpotential deposition (UPD) on Ni surface from 0.2 M HClO4 solution
containing 10-3 M Sn2+ with relation to the inhibition effect of Sn on aqueous
corrosion of Ni. The periodical emersion method under potentiostatic polarization,using the surface-roughened Ni plate (surface roughness S-r = 78.3) as a working
electrode was employed to detect sensitively the sub-monolayer coverage of Sn on
Ni. The Sn K-edge absorption spectra in a scanning XAS mode were measured bymonitoring the Sn K-alpha 1 fluorescence line. The Sn K-edge absorption nearedge structure (XANES) in the Sn-UPD potential region has revealed that the SnUPD layer on Ni is oxygenated. The extended X-ray absorption fine structure(EXAFS) analysis was performed with a two shell fit of the nearest neighbor SnNi and Sn-O interactions, assuming that the uppermost Ni surface exposed to thesolution is mainly oriented to the (111) plane. The results have indicated that Sn
atoms are substituted like a surface alloy at face- center-cubic sites in the first Ni
layer and further bonded with oxygen atoms. The strong inhibition effect of Sn on
aqueous corrosion of Ni is ascribed to the bond between Sn and O atoms in. addition
to the bond between Sn and Ni atoms.

59Electrochemical Analysis of Hydrogen Membrane Fuel
Cells with Amorphous Zirconium Phosphate Thin Film
Electrolyte
R. Nonaka, Y. Aoki, E. Tsuji, S. Nagata and H. HabazakiElectrochemistry, 82, 859-864 (2014)
An electrochemical analysis was conducted with respect to a hydrogenmembrane fuel cell (HMFC) comprising proton-conducting, amorphous zirconium
phosphate, a-ZrP2.5O8.9H1.3, thin film electrolyte supported on a dense Pd anode.
The HMFC gave rise to an OCV of 1.0 V, but the maximum power density was
limited and was about 1 mW cm-2 at 400C. The impedance spectroscopy revealed
that the interfacial polarizations were decreased by two orders of magnitude when
the cell configuration was changed from the fuel cell setup to the hydrogenconcentration cell with an anode symmetric configuration. These results indicatedthat the polarization losses at the solid-solid anode interface are not a main
contribution to the voltage loss of the HMFC. The large cathode polarization might
be attributed to the lessened conductivity of amorphous zirconium phosphateelectrolyte thin film formed on a precious metal electrode.

60Fabrication of Superoleophobic Hierarchical Surfaces for
Low-surface-tension Liquids
K. Nakayama, E. Tsuji, Y. Aoki and H. Habazaki
RSC Advances, 4, 30927-30933 (2014)
This study demonstrates the fabrication of hierarchical surfaces withsuper-repellency even for low-surface-tension liquids, including octane (surface
tension of 21.7 mN m-1). Dual-pore surfaces were prepared by a combination ofpractical wet processes on an aluminium substrate: chemical etching, anodizing,and organic monolayer coating. The size of the larger pores formed by the chemical
etching of aluminium is controlled by the concentration of HCl in the CuCl2/HCletching solution. The etched aluminium is then anodized to introduce nanopores,
followed by a pore-widening treatment that controls the nanopore size and porosity.
The repellency for low-surface-tension liquids is enhanced by increasing the sizeof the larger pores as well as the porosity of the walls of the larger pores in thisdual-pore morphology. Under optimized morphology with a fluoroalkyl-phosphatemonolayer coating, an advancing contact angle close to 160, a contact angle
hysteresis of less than 5[degree] and a sliding angle of 10  is achieved even foroctane.

61

Formation-structure-properties of Niobium-oxide
Nanocolumn Arrays via Self-organized Anodization of
Sputter-deposited Aluminum-on-niobium Layers
A. Mozalev, R. M. Vazquez, C. Bittencourt, D. Cossement, F. Gispert-Guirado,
E. Llobet and H. Habazaki
Journal of Materials Chemistry C, 2, 4847-4860 (2014)
Nanostructured niobium oxide (NO) semiconductors are gaining
increasing attention as electronic, optical, and electro-optic materials. However,the preparation of stable NO nanofilms with reproducible morphology and behavior
remains a challenge. Here we show a rapid, well-controlled, and efficient way tosynthesize NO films with self-organized columnlike nanostructured morphologies
and advanced functional properties. The films are developed via the growth of ananoporous anodic alumina layer, followed by the pore-directed anodization of the
Nb underlayer. The columns may grow 30-150 nm wide, up to 900 nm long, withan aspect ratio of up to 20, being anchored to a thin continuous oxide layer that
separates the columns from the substrate. The as-anodized films have a gradedchemical composition changing from amorphous Nb 2O5 mixed with Al2O3, Si-, andP-containing species in the surface region to NbO2 in the lower film layer. The postanodization treatments result in the controlled formation of Nb2O5, NbO2, and NbO
crystal phases, accompanied by transformation from nearly perfect dielectric to ntype semiconductor behavior of the films. The approach allows for the smooth film
growth without early dielectric breakdown, stress-generated defects, or destructive
dissolution at the respective interfaces, which is a unique situation in the oxide
films on niobium. The functional properties of the NO films, revealed to date, allow
for potential applications as nanocomposite capacitor dielectrics and active layers
for semiconductor gas microsensors with the sensitivity to ethanol and the response
to hydrogen being among best ever reported.

62

Nanostructured Anodic-alumina-based Dielectrics forHigh-frequency Integral Capacitors
A. Mozalev, M. Sakairi, H. Takahashi, H. Habazaki and J. Hubálek
Thin Solid Films, 550, 486-494 (2014)
Three types of thin solid films with the nanoscale inner structures weresynthesized by sputtering-deposition and anodizing of Al layer, Al-1.5 at.% Sialloy layer, and Al/Ta bilayer on Si wafers. All the anodic films comprised 1 μm
thick nanoporous alumina layer as the key component. The essential differenceswere due to the silicon impurities (AlSi alloy) and the array of nanosized tantalumoxide protrusions in the alumina barrier layer (Al/Ta bilayer). The films were
examined by scanning and transmission electron microscopy and electrochemical
impedance spectroscopy. Integral capacitors utilizing the anodic films as dielectrics
combine the small-value capacitance (6.5 nF cm− 2) with the excellent propertiesof high withstand field strength (1.7–2.7 MV cm− 1), low leakage current ((3–20)
× 10− 12 A mm− 2 at 1.0 MV cm− 1), and low loss tangent (tgδ = (4–6) × 10− 3). The
revealed dispersion of dielectric constant, although within 10%, and the presenceof loss peaks on the temperature and frequency dependencies of tgδ denote theinfluence of ion-relaxation mechanism on dielectrics' polarizability, with thecharacteristic times ranging from 10 to 145 μs depending on the dielectric type. By
selecting appropriate technological and electrolytic conditions, the functionality of
the capacitors can be optimized to meet the needs of a specific range, from 1 kHz
to about 300 MHz operating frequencies.

63Characterization of Self-Assembled Monolayer on
Anodized Aluminum by XPS, AFM and Low-Voltage SEM
H. Habazaki, H. Sato, E. Tsuji, Y. Aoki and K. Shimizu
ECS Transactions, 58, 75-83 (2014)
Organic layers of tetradecylphosphonic acid (TDP) and
octadecyltrietoxysilane (OES) are formed on flat anodized aluminum surfaces bya simple immersion process. The organic layers are characterized by dynamic
contact angle measurements for water, AFM, low-voltage SEM and angle- resolved
XPS. The results indicate that a self-assembled monolayer is formed using TDP,
but not for OES. Plasma surface treatment prior to the coating was found to
significantly influence the formation of organic layers.

64

The Effects of Film Thickness and Incorporated Anions
on Pitting Corrosion of Aluminum with Barrier-type
Oxide Films Formed in Neutral Borate and Phosphate
Electrolytes
H. Habazaki, R. Nishimura, K. Okitsu, H. Inoue, I. Kiriyama, F. Kataoka,
M. Sakairi and H. Takahashi
Journal of Solid State Electrochemistry, 18, 369-376 (2014)
The pitting corrosion behavior of high-purity aluminum covered withbarrier-type anodic films, which are formed in neutral borate and phosphateelectrolytes, has been examined in 0.5 mol dm-3 NaCl solution at an applied
potential of -0.6 V versus Ag/AgCl, which is slightly nobler than the pitting
potential of -0.64 V in the same solution. The pitting current density, ip, increased
with time after an incubation time, ti. The double logarithmic plot of ip andpolarization time, t, reveal two straight lines, which are separated at the time, tau.
The slope becomes larger after tau for the specimens anodized in the phosphateelectrolyte, while it becomes smaller for those in the borate electrolyte. Both the ti.
and tau increase with the thickness of the anodic films, and at the similar film
thickness, they are much larger for the anodic films formed in the phosphateelectrolyte than for those in the borate electrolyte. The corrosion process can bedivided into three stages: the incubation period up to ti, the pit nucleation period
before tau, and the pit growth period after tau. We have discussed the different
pitting corrosion behavior of the aluminum specimens covered with the anodic
films formed in the borate and phosphate electrolytes in terms of ion selectivity of
the anodic films.

65

Highly Enhanced Corrosion Resistance of StainlessSteel by Sol-Gel Layer-by-Layer Aluminosilicate Thin
Coatings
H. Habazaki, T. Kimura, Y. Aoki, E. Tsuji and T. Yano
Journal of the Electrochemical Society, 161, C57-C61 (2014)
In this study, aluminosilicate sol-gel coatings were deposited on Type430 stainless steel by multiple spin casting cycles. Amorphous aluminosilicate
coatings, 65 nm thick, were prepared from precursor solutions with 50, 100, and
500 mmol dm−3 total concentrations of aluminum and silicon species (molar ratioof Al/Si = 1/4) by 10, 5, and 1 spin casting cycles, respectively. Although theobtained coatings had a similar composition with a molar ratio of Al/Si = 25/75,
the coatings with increased density were formed by reducing the concentration of
precursor solution. The pitting potentials of the coated stainless steels, measured
by potentiodynamic polarization in 3.5% NaCl solution, increased remarkably (to1.1 V vs Ag/AgCl) with a decrease in the concentration of precursor solution.
Cyclic corrosion tests, consisting of 30 cycles of spraying of 5% NaCl solution at
35°C for 2 h, drying at 60°C for 4 h, and wetting at 50°C and >95% relative
humidity for 2 h, revealed highly improved corrosion resistance. Layer-by-layer
sol-gel deposition using diluted precursor solutions is an effective way to obtainhighly protective coatings.

66

Efficient Growth of Anodic Films on Magnesium in
Organic Electrolytes Containing Fluoride and Water
H. Habazaki, F. Kataoka, E. Tsuji, Y. Aoki, S. Nagata, P. Skeldon and
G. E. Thompson
Electrochemistry Communications, 46, 30-32 (2014)
Abstract the present study reports, for the first time, the highly efficient
formation of barrier-type anodic films, with flat and parallel metal/film andfilm/electrolyte interfaces, on magnesium in ethylene glycol electrolytes
containing ammonium fluoride and water. The anodizing voltage increases linearlywith time during galvanostatic anodizing at 10 A m−2 up to 350 V. The anodic film
formed to 200 V is 247 nm thick, containing a crystalline MgF 2 phase. Analysis by
Rutherford backscattering spectroscopy discloses the film composition of
MgF1.8O0.1 and Pilling–Bedworth ratio (PBR) of 1.67. The PBR value greater thanunity and the formation of chemically stable fluoride-based films may contributeto the film growth at high current efficiency.

67

Mixed Proton Electron Conductivity of Calcium
Chromate(V) Apatite
Y. Aoki, K. Kikutani, E. Tsuji and H. Habazaki
ECS Electrochemistry Letters, 3, F61-F64 (2014)
This is the first report to investigate on the electrical conductivity ofunusual high valence state pentavalent chromium oxides in terms of defectthermodynamics. Calcium chromium(V) apatite was prepared as a single phase,and the electrical conductivity was examined as a function of oxygen partialpressure pO2. The conductivity was increased at higher pO2 in wet atmosphere but it
was not dependent on pO2 in dry atmosphere. The water concentration cell gives
stable electromotive force. The features disclosed that the chromium(V) apatite
reveals proton electron mixed conductivity under wet oxidative condition.

Electrochemical Properties of Heated Carbon Nanofibers
for Lithium Ion Capacitor
S.-K. Ahn, J.-J. Yang, H.-I. Kim, H. Habazaki and S.-G. Park
Chemistry Letters, 43, 898-900 (2014)
We have investigated the effects of heat treatment on theelectrochemical properties of carbon nanofibers (CNFs) for use as an anodematerial in lithium ion capacitors. The CNFs were fabricated by liquid-phasecarbonization on a porous alumina template that was anodized in oxalic acid at 40
V for 30 min and subjected to a pore-widening process in phosphoric acid at room
temperature. The CNFs were heated at temperatures of 600, 1000, and 1400 °C tofacilitate rearrangement of the carbon structure.
]68Bulk Mixed Ion Electron Conduction in Amorphous
Gallium Oxide Causes Memristive Behavior
Y. Aoki, C. Wiemann, V. Feyer, H.-S. Kim, C. M. Schneider, H. Ill-Yoo and
M. Martin
Nature communications, 5, 3473/1-/9 (2014).
In thin films of mixed ionic electronic conductors sandwiched by two
ion-blocking electrodes, the homogeneous migration of ions and their polarization
will modify the electronic carrier distribution across the conductor, thereby
enabling homogeneous resistive switching. Here we report non-filamentary
memristive switching based on the bulk oxide ion conductivity of amorphous GaOx
(x~1.1) thin films. We directly observe reversible enrichment and depletion ofoxygen ions at the blocking electrodes responding to the bias polarity by using
photoemission and transmission electron microscopies, thus proving that oxygenion mobility at room temperature causes memristive behaviour. The shape of thehysteresis I-V curves is tunable by the bias history, ranging from narrow counter8 figure loops to wide-hysteresis, triangle loops as found in the mathematicallyderived memristor model. This dynamical behaviour can be attributed to thecoupled ion drift and diffusion motion and the oxygen concentration profile acting
as state function of the memristor.

69

Effect of Sn2+ on Anodic Dissolutionof Ni in Perchloric Acid
Masahiro Seo, Atsushi Hyono, Hiroki Habazaki and Takenori Nakayama
Journal of the Electrochemical Society, 161, C550-C556 (2014)
The effect of Sn2+ on anodic dissolution of nickel was investigated indeaerated 0.2 M HClO4 solution containing Sn2+ at room temperature. It has beenfound that the addition of 10 -3 M Sn2+ inhibits completely the anodic dissolution of
Ni. In contrast, tin itself is not passivated in 0.2 M HClO4 irrespective of theaddition of 10-3 M Sn2+. Besides, the anodic dissolution of Ni is not inhibited by thesurface coating with Sn (IV) colloid which mainly consisting of hydrous oramorphous nano-crystalline SnO2. X-ray photoelectron spectroscopy (XPS)
analysis used to supplement our recent X-ray absorption spectroscopy (XAS)
results has indicated that the inhibition effect of Sn2+ on anodic dissolution of Ni is
associated with the underpotential deposition (UPD) of Sn on Ni. The metallic bond
between Sn and Ni in Sn-UPD layer on Ni is prerequisite to the formation of Sn(II) residue adhesive to the Ni substrate at the more noble potential that brings theinhibition effect on anodic dissolution of Ni. Moreover, the difference between
inhibition effects of Sn2+ and Pb2+ on anodic dissolution of Ni was discussed on
basis of the difference between Sn- and Pb-UPD on Ni.

70Fabrication of a Micro-Porous Ti-Zr Alloy by Electroless
Reduction with a Calcium Reductant for Electrolytic
Capacitor Applications
Tatsuya Kikuchi, Masumi Yoshida, Yoshiaki Taguchi, Hiroki Habazaki and
Ryosuke O. Suzuki,
Journal of Alloys and Compounds, 586, 148-154 (2014)
A metallic titanium and zirconium micro-porous alloy for electrolytic
capacitor applications was produced by electroless reduction with a calcium
reductant in calcium chloride molten salt at 1173 K. Mixed TiO2–70 at%ZrO2oxides, metallic calcium, and calcium chloride were placed in a titanium crucible
and heated under argon atmosphere to reduce the oxides with the calcium reductant.
A metallic Ti–Zr alloy was obtained by electroless reduction in the presence ofexcess calcium reductant and showed a micro-porous morphology due to thesintering of each of the reduced particles during the reduction. The residual oxygen
content and surface area of the reduced Ti–Zr alloy decreased over time during theelectroless reduction. The element distributions were slightly different at thepositions of the alloy and were in the composition range of Ti-69.3 at% to 74.3
at%Zr. A micro-porous Ti–Zr alloy with low oxygen content (0.20 wt%) and large
surface area (0.55 m2 g−1) was successfully fabricated by electroless reduction
under optimal conditions. The reduction mechanisms of the mixed and pure oxides
bythecalcium
reductantarealso
discussed.
dx.doi.org/10.1016/j.jallcom.2013.10.052

71Fabrication of Anodic Porous Alumina
by Squaric Acid Anodizing
Tatsuya Kikuchi, Tsuyoshi Yamamoto, Shungo Natsui and Ryosuke O. Suzuki
Electrochimica Acta, 123, 14-22 (2014)
The growth behavior of anodic porous alumina formed via anodizing
in a new electrolyte, squaric acid (3,4-dihydroxy-3-cyclobutene-1,2-dione), isreported for the first time. A high-purity aluminum foil was anodized in a 0.1 M
squaric acid solution at 293 K and a constant applied potential of 100-150 V.
Anodic oxides grew on the aluminum foil at applied potentials of 100-120 V, but
a burned oxide film was formed at higher voltage. Anodic porous alumina with acell size of approximately 200–400 nm and sub-100-nm-scale pore diameter was
successfully fabricated by anodizing in squaric acid. The cell size of the anodic
oxide increased with anodizing time because of the uneven growth of the porous
layer. The anodic porous alumina obtained by squaric acid anodizing consists ofamorphous Al2O3 containing 5-6 at% carbon from the electrolyte.
dx.doi.org/10.1016/j.electacta.2013.12.186

72

Rapid Reduction of Titanium Dioxide Nano-particles by
Reduction with a Calcium Reductant
Tatsuya Kikuchi, Masumi Yoshida, Shiki Matsuura, Shungo Natsui, Etsuji
Tsuji, Hiroki Habazaki and Ryosuke O. Suzuki
Journal of Physics and Chemistry of Solids, 75, 1041-1048 (2014)
Micro-, submicron-, and nano-scale titanium dioxide particles werereduced by reduction with a metallic calcium reductant in calcium chloride molten
salt at 1173 K, and the reduction mechanism of the oxides by the calcium reductant
was explored. These oxide particles, metallic calcium as a reducing agent, andcalcium chloride as a molten salt were placed in a titanium crucible and heatedunder an argon atmosphere. Titanium dioxide was reduced to metallic titanium
through a calcium titanate and lower titanium oxide, and the materials weresintered together to form a micro-porous titanium structure in molten salt at hightemperature. The reduction rate of titanium dioxide was observed to increase withdecreasing particle size; accordingly, the residual oxygen content in the reduced
titanium decreases. The obtained micro-porous titanium appeared dark gray incolor because of its low surface reflection. Micro-porous metallic titanium with alow oxygen content (0.42 wt%) and a large surface area (1.794 m2 g−1) can be
successfully
obtainedbyreduction
under
optimalconditions.
dx.doi.org/10.1016/j.jpcs.2014.04.016

73

Fabrication of Anodic Nanoporous Alumina via
Acetylenedicarboxylic Acid Anodizing
Tatsuya Kikuchi, Osamu Nishinaga, Shungo Natsui and Ryosuke O. Suzuki
ECS Electrochemistry Letters, 3, C25-C28 (2014)
The nano-morphologies of anodic porous alumina formed via anodizing
in a new electrolyte, acetylenedicarboxylic acid (ADCA), are described. Anodic
oxides grew uniformly on the aluminum at voltage of 87.5–95.0 V, but a burned
black oxide film was formed at higher voltage. The burning voltage and the current
density under steady-state oxide growth decreased with solution temperature. An
anodic porous alumina film with a cell size of 250 nm and nanopores measuring
100 nm could be successfully obtained by ADCA anodizing. The anodic porousalumina possessed numerous non-straight nanopores due to the branching andextinction of the nanopores during anodizing. dx.doi.org/10.1149/2.0071407eel

74

Fabrication of Anodic Porous Alumina via Anodizing
in Cyclic Oxocarbon Acids
Tatsuya Kikuchi, Daiki Nakajima, Jun Kawashima, Shungo Natsui and
Ryosuke O. Suzuki
Applied Surface Science, 313, 276-285 (2014)
The growth behavior of anodic porous alumina formed by anodizing
in novel electrolyte solutions, the cyclic oxocarbon acids croconic and rhodizonicacid, was investigated for the first time. High-purity aluminum specimens wereanodized in 0.1 M croconic and rhodizonic acid solutions at various constantcurrent densities. An anodic porous alumina film with a cell size of 200 –450 nm
grew uniformly on an aluminum substrate by rhodizonic acid anodizing at 5– 40
A m−2, and a black, burned oxide was formed at higher current density. The cellsize of the porous alumina increased with current density and corresponding
anodizing voltage. Anodizing in croconic acid at 293 K caused the formation ofthin anodic porous alumina films as well as black, thick burned oxides. The
uniformity of the porous alumina improved by increasing the temperature of thecroconic acid solution, and anodic porous alumina films with a uniform film
thickness were successfully obtained. Our experimental results showed that thecyclic oxocarbon acids croconic and rhodizonic acid could be employed as asuitable electrolyte for the formation of anodic porous alumina films.
dx.doi.org/10.1016/j.apsusc.2014.05.204

75

Self-Ordering Behavior of Anodic Porous Alumina via
Selenic Acid Anodizing
Tatsuya Kikuchi, Osamu Nishinaga, Shungo Natsui and Ryosuke O. Suzuki
Electrochimica Acta, 137, 728-735 (2014)
The self-ordering behavior of anodic porous alumina that was formedby anodizing in selenic acid electrolyte (H2SeO4) at various concentrations andvoltages was investigated with SEM and AFM imaging. A high purity aluminum
foil was anodized in 0.1-3.0 M selenic acid solutions at 273 K and at constant cellvoltages in the range of 37 to 51 V. The regularity of the cell arrangement increased
with increasing anodizing voltage and selenic acid concentration under conditionsof steady oxide growth without burning. Anodizing at 42 -46 V in 3.0 M selenicacid produced highly ordered porous alumina. By selective dissolution of theanodic porous alumina, highly ordered convex nanostructures of aluminum withdiameters of 20 nm and heights of 40 nm were exposed at the apexes of eachhexagonal dimple array. Highly ordered anodic porous alumina with a cell size of
102 nm from top to bottom can be fabricated by a two-step selenic acid anodizing
process, that includes the first anodizing step, the selective oxide dissolution, andthe second anodizing step. dx.doi.org/10.1016/j.electacta.2014.06.078

76Growth Behavior of Anodic Oxide Formed by Aluminum
Anodizing in Glutaric and Its Derivative Acid Electrolytes
Daiki Nakajima, Tatsuya Kikuchi, Shungo Natsui and Ryosuke O. Suzuki
Applied Surface Science, 321, 364-370 (2014)
The growth behavior of anodic oxide films formed via anodizing inglutaric and its derivative acid solutions was investigated based on the aciddissociation constants of electrolytes. High-purity aluminum foils were anodized
in glutaric, ketoglutaric, and acetonedicarboxylic acid solutions under various
electrochemical conditions. A thin barrier anodic oxide film grew uniformly on thealuminum substrate by glutaric acid anodizing, and further anodizing caused thefilm to breakdown due to a high electric field. In contrast, an anodic porous alumina
film with a submicrometer-scale cell diameter was successfully formed by
ketoglutaric acid anodizing at 293 K. However, the increase and decrease in thetemperature of the ketoglutaric acid resulted in non-uniform oxide growth andlocalized pitting corrosion of the aluminum substrate. An anodic porous alumina
film could also be fabricated by acetonedicarboxylic acid anodizing due to therelatively low dissociation constants associated with the acid. Acid dissociation
constants are an important factor for the fabrication of anodic porous alumina films.
dx.doi.org/10.1016/j.apsusc.2014.10.014

77Ultra-High Density Single Nanometer-Scale Anodic
Alumina Nanofibers Fabricated by Pyrophosphoric Acid
Anodizing
Tatsuya Kikuchi, Osamu Nishinaga, Daiki Nakajima, Jun Kawashima,
Shungo Natsui, Norihito Sakaguchi and Ryosuke O. Suzuki,
Scientific Reports, 4, 7411 (2014)
Anodic oxide fabricated by anodizing has been widely used fornanostructural engineering, but the nanomorphology is limited to only two oxides:
anodic barrier and porous oxides. Therefore, the discovery of an additional anodic
oxide with a unique nanofeature would expand the applicability of anodizing. Here
we demonstrate the fabrication of a third-generation anodic oxide, specifically,anodic alumina nanofibers, by anodizing in a new electrolyte, pyrophosphoric acid.
Ultra-high density single nanometer-scale anodic alumina nanofibers (10 10
nanofibers/cm2) consisting of an amorphous, pure aluminum oxide weresuccessfully fabricated via pyrophosphoric acid anodizing. The nanomorphologiesof the anodic nanofibers can be controlled by the electrochemical conditions.
Anodic tungsten oxide nanofibers can also be fabricated by pyrophosphoric acidanodizing. The aluminum surface covered by the anodic alumina nanofibers
exhibited ultra-fast superhydrophilic behavior, with a contact angle of less than 1°,
within 1 second. Such ultra-narrow nanofibers can be used for various
nanoapplications including catalysts, wettability control, and electronic devices.
dx.doi.org/10.1038/srep07411

78

Porous Anodic Oxide Films on Aluminum and Their
Nanofabrication (Review)
Tatsuya Kikuchi, Daiki Nakajima, Osamu Nishinaga, Shungo Natsui and
Ryosuke O. Suzuki,
Journal of Japan Institute of Light Metals, 64, 476-482 (2014)
In this review article, we introduce the fundamentals of barrier andporous type anodic oxide films formed via anodizing of aluminum. We also
introduce the various electrolyte species used for porous alumina fabrication anddescribe the self-ordering conditions during anodizing in these electrolyte
solutions. Highly ordered anodic porous alumina can be successfully fabricated via
anodizing under the optimum electrochemical conditions. Various
nanoapplications using ordered porous alumina such as optical and electronic
devices are also introduced.
dx.doi.org/10.2464/jilm.64.476

79

Multiphase Particle Simulation of Gas Bubble Passing
through Liquid/Liquid Interfaces
Shungo Natsui, Hifumi Takai, Takehiko Kumagai, Tatsuya Kikuchi and
Ryosuke O. Suzuki,
Materials Transactions, 55, [11] 1707-1715 (2014)
A newly developed computational fluid dynamics (CFD) model basedon a multi-phase particle method is presented for predicting the entrainment
behavior of liquid metal into slag due to rising single bubble. By comparing results
calculated using this model against experimental data, it was found that thetransient behavior of bubbles and the two immiscible liquids can be accurately
estimated by this method. The rupturing of the thin water film surrounding the
bubble was less reliably predicted, but this 3-dimensional unsteady numericalmodel still nevertheless provides valuable new information for directly predicting
the change in the liquid/liquid interface over time. Such prediction of continuouschange in an interface has not been possible by more conventional methods, andthus further improvement in the accuracy of this simulated model may well be theonly way to non-empirically predict the metal-slag interface area in actual
processes.
dx.doi.org/10.2320/matertrans.M2014245

80

Numerical Analysis of Carbon Monoxide-Hydrogen Gas
Reduction of Iron Ore in a Packed Bed by an EulerLagrange Approach
Shungo Natsui, Tatsuya Kikuchi and Ryosuke O. Suzuki
Metallurgical and Materials Transactions B, 45, [6] 2395-2413 (2014)
In recent years, various methods to decrease carbon dioxide emissions
from iron and steel making industries have been developed. The latest blast furnace
operation design is intended to induce the low reducing agent operation, highly
reactive material is considered a promising way to improve reaction efficiency.
Another method utilizes hydrogen in the blast furnace process for highly efficient
reduction. Mathematical modeling may help to predict complex in-furnace
phenomena, including momentum, heat, and mass transport. However, the current
macroscopic continuum model gives no information on the individual particles. In
this work, a new approach based on the discrete element method was introduced toconsider the interaction between particles under fluid flow in accordance with thearrangement and properties of individual particles. We used an Euler–Lagrange
method to precisely understand the influence of the reaction conditions on the
behavior of coke and ore particles in three dimensions. The heterogeneity of thereaction rate and temperature distribution was observed to be influenced by theparticle arrangement. The endothermic and exothermic reactions influenced eachother in the packed bed. Temperature distributions nearly correlated with the gas
velocity distribution because convection processes greatly affected the reaction
rate. Although convection heat transfer was not a dominant issue in the packed bed,
promotion of the reaction by a gas flow was effective.
dx.doi.org/10.1007/s11663-014-0132-x

81

Stable Mesh-free Moving Particle Semi-implicit Method
for Direct Analysis of Gas-Liquid Two-Phase Flow
Shungo Natsui, Hifumi Takai, Takehiko Kumagai, Tatsuya Kikuchi and
Ryosuke O. Suzuki,
Chemical Engineering Science, 111, 286-298 (2014)
In a metallurgical process, gas–liquid flow plays an important role inincreasing the efficiency by stirring liquid mechanically or by injecting a gas.
Owing to the difficulty of direct observation in a high-temperature system or real
furnace experiment, numerical analysis is useful and widely studied. However,
flexible treatment of complicated free surface behavior such as fragmentation andcoalescence of liquids is still a difficult problem. This paper presents a newparticle-based simulation scheme for gas–liquid flow. We improved the numericalstability, which is generally a problem with the particle method, and verified themodel’s accuracy for fundamental gas–liquid flow analysis.
Because all the phases were discretized as particles in Moving Particle
Semi-implicit (MPS) method, the proposed model can track the movement of both
the gas and liquid phases directly. A large difference in the real density between
the gas and liquid phases makes the gas–liquid interface behavior unstable. This
study proposed an optimization of the weakly compressible Poisson equation, an
initial particle arrangement, and a smoothed interface density in order to stabilize
the multi-density flow analysis. This model guarantees conservation of the fluid
volume even for a high-density-ratio flow like that at a gas–liquid interface.
Therefore, a gas–liquid interface has been represented with high accuracy. We
believe that this scheme is also applicable to phenomena in an actual process that
includes many dispersal phases.
dx.doi.org/10.1016/j.ces.2014.02.038

82

Ionic Conduction of Oxygen and Calciothermic
Reduction in Molten CaO-CaCl2
Ryosuke O. Suzuki, Daisuke Yamada, Shogo Osaki,
Reyna F. Descallar-Arriesgado and Tatsuya Kikuchiin "Molten Salts Chemistry and Technology", ed. by Marcelle Gaune-Escard,
Geir Martin Haarberg, John Wiley & Sons, Chichester, West Sussex, UK,
ISBN: 978-1-118-44873-1 (2014) pp.115-122.
Oxygen conductive nature of CaO-CaCl2 melt was confirmed by EMF
method at the high oxygen partial pressure, PO2 >10-19 atm at 1073-1173 K, while
the stable EMF could not be obtained at the low PO2. A disk of the oxygen
conductive La0.8Sr0.2Ga0.8Mg0.15Ni0.05O3 or La0.8Sr0.2Ga0.8Mg0.2O3 was used as theoxygen absorbing anode. The reduction of NiO powder to metallic Ni at cathodeand the simultaneous O2 gas evolution inside the anode indicate the oxygen ionic
conduction in the used ceramic pellets as well as in the molten salt. The electricisolation of the NiO powder from the cathode confirmed that the calciothermic
reduction occurs through the electrolysis of CaO in the CaCl2 melt, which is also
verifiedbytheCaO
concentration
dependency
ofcurrent.
dx.doi.org/10.1002/9781118448847.ch2a83

Thermoelectric Analysis
for Helical Power Generation Systems
Xiangning Meng, Takeyuki Fujisaka and Ryosuke O. Suzuki
J. Electron. Mater., 43, [6] 1509-1520 (2014)
The performance of a three-dimensional helical thermoelectric
generation (TEG) system is examined by exposing it to a temperature differencewith hot and cold sources. The helical paths for the two thermal fluids give the TEG
device the potential to efficiently convert thermal energy. The characteristic
performance of the helical system is numerically analyzed by using the finite volume method in a compact system. The helical system is compared with a straightsystem in which all the thermoelectric (TE) elements present equivalent geometry.
The difference in the TE performance between the two systems is not significant
when the TE surfaces are maintained at constant temperatures. Both theelectromotive force and the current in the TEG system increase linearly with thetemperature difference ΔT applied at the two module surfaces. The current
preferentially flows through a main path determined by the geometry of the TE
element. The merits of the helical design are its compactness, space saving, andsmooth fluid flow due to gravity, compared with the straight system.
dx.doi.org/10.1007/s11664-013-2768-8

84

Thermoelectric Analysis for Pai-type Thermoelectric
Module with Tilted Elements
Xiangning Meng, Takeyuki Fujisaka, Keita O. Ito and Ryosuke O. Suzuki
Materials Research Innovations, 18, Suppl.4, S4-116-121 (2014)
Thermoelectric (TE) legs in the Π-type module for TE generation aretilted as a shape of parallelogram, and three-dimensional flows of heat and electriccharge are examined by using a numerical analysis of finite-volume method. The
distributions of temperature and current density are significantly dependent on themodule configuration and leg shape. The shortest path is chosen preferentially as
mainstream of current. The Π-type module is the most favorable because themaximum performance is obtained in case that the tilting angle is 90°. Under theconstant temperature difference, the charge-transporting ability of the stream isgoverned by the path length.
dx.doi.org/10.1179/1432891714Z.000000000654

85

Thermoelectric Analysis for a Three-Dimensional Power
Generator in Helical
Xiangning Meng, Takeyuki Fujisaka, Keita O. Ito and Ryosuke O. Suzuki
Key Engineering Materials, 617, 260-264 (2014)
Thermoelectric (TE) phenomenon of a helical generator is numericallyanalyzed by using the finite-volume method in combination with a threedimensional finite-element (FE) model. The distributions of temperature andcurrent density are significantly influenced by the generator dimension. The output
power of helical generator is also affected by the geometric parameter, such as thehelical pitch. The output power and conversion efficiency of helical generator are
better than those of straight generator where all the TE elements aligned in astraight line. The helical geometry has a satisfactory potential to be a good TE
generator.
dx.doi.org/10.4028/www.scientific.net/KEM.617.260

86

Optimization of Module Shape in Thermoelectric Power
Generation
Ryosuke O. Suzuki and Takeyuki Fujisaka
Key Engineering Materials, 617, 251-255 (2014)
Heat and electric charge transfer through the thermoelectric (TE)module were analyzed numerically. The thermal heat can expand or shrink in the
trapezoid shape in comparison with the conventional Π type module, and the output
and efficiency from the module with trapezoid TE elements was examined from theview of shape optimization. The temperature profile and some thermoelectric
properties were calculated using the infinite volume method and the original code.
The temperature profile in the module showed a complex distribution in the TE
elements, however, the efficiency in power generation did not change from that of
the rectangular TE module.
dx.doi.org/10.4028/www.scientific.net/KEM.617.251

87

Light-Concentration Characteristic of Water Lens and its
Application to Thermoelectric Generation
Keita O. Ito, Hongtao Sui, Hidetoshi Hakozaki, Hiroshi Kinoshita and
Ryosuke O. Suzuki
Key Engineering Materials, 617, 247-250 (2014)
A water lens was used to concentrate sunlight on the surface of athermoelectric (TE) module in order to heat it. The shape of this water lens could
be flexibly adjusted to compensate for solar altitude changes. The light condensed
by the water lens produced a large energy distribution on the top of the module. In
this study, we simulated the power generation properties when the top of the module
was heated by light with a certain condensing distribution. The simulation results
revealed that the energy distribution had little effect on the TE generation if thesolar light was effectively condensed on a plate with a condensing width of a few
millimeters.
dx.doi.org/10.4028/www.scientific.net/KEM.617.247

88Simulation of a thermoelectric module having
parallelogram elements
Xiangning Meng, Takeyuki Fujisaka, Keita O. Ito and Ryosuke O. Suzuki
Materials Transaction, 55, [8] 1219-1225 (2014)
A thermoelectric (TE) module with two different thermal sources for
power generation is studied in this work. Here, a conventional Π-type module istilted in the shape of a parallelogram. A numerical analysis is conducted by using
the finite volume method to examine three-dimensional (3-d) flows of heat andelectric charge. The module configuration and the shape of the elements determine
the distribution of temperature and current density inside the TE module. Further,
the shortest path is chosen preferentially as the path of the current, depending on
the geometry of the TE elements. Although the distribution of current density
depends greatly on the module configuration, the TE output power is not affectedby the parallel and symmetrical configurations in the two equivalent modules. Thus,
the conventional TE module with Π-type elements is the most favorable, andmaximum performance is obtained for a tilting angle of 90° because of the lowest
internal electric resistance. dx.doi.org/10.2320/matertrans.E-M2014822

89

New n-type Silicide Thermoelectric Material with High
Oxidation Resistance
Ryoji Funahashi, Yoko Matsumura, Tomonari Takeuchi, Hideaki Tanaka,
Wataru Norimatsu, Emmanuel Combe, Ryosuke O. Suzuki, Chunlei Wan,
Yifeng Wang, Michiko Kusunoki and Kunihito Koumoto
Mater. Res. Soc. Symp. Proc. 1490, [1] 103-112 (2013)
In order to achieve waste heat recovery using thermoelectric systems,
thermoelectric materials showing high conversion efficiency over wide
temperature range and high resistance against oxidation are indispensable. A
silicide material with good n-type thermoelectric properties and oxidation
resistance has been discovered. The composition and crystal structure of thesilicide are found out Mn3Si4Al2 (abbreviated as 342 phase) and hexagonal CrSi2
structure, respectively. Element substitution of Mn with 3d transition metals is
succeeded. Enhancement of Seebeck coefficient is observed in a Cr-substituted
sample. The maximum dimensionless thermoelectric figure of merit ZT is 0.3 at
573 K in air for the Mn2.7Cr0.3Si4Al2 sample. Electrical resistivity of the Mn 3Si4Al2
bulk sample holds constant value for 48 h at 873 K in air. This is due to formationof oxide passive layer on the surface of the bulk sample. The 342 phase is apromising n-type material with a good oxidation resistance in the middle
temperature range of 500-800 K.
dx.doi.org/10.1557/opl.2013.117

90

Using a Water Lens for Light Concentration in
Thermoelectric Generation
Keita O. Ito, Hongtao Sui, Hidetoshi Hakozaki, Hiroshi Kinoshita and
Ryosuke O. Suzuki
J. Electr. Mater., 43, [6] 2086-2093 (2014)
A water lens is employed to concentrate sunlight on the surface of athermoelectric module in order to heat it. This water lens can change its shapeflexibly and is adjustable to solar altitudes. The lens shape and light path were
simulated for the cases when the light is incident at an angle to the water surface,parallel to the central axis of the half-cylindrical water lens, and when the light isfocused on a plate. A condensing ratio larger than 70 is achieved when the incident
light is closer to the normal of the water surface and if the optimal lens shape ismaintained.
dx.doi.org/10.1007/s11664-013-2965-5

91Effects of Nano Metal Coatings on Growth Kinetics of αAl2O3 Formed on Ni-50Al Alloy
A. Shaaban, S. Hayashi, K. Azumi

Oxidation of Metals 82:85-97 (2014).

The effects of pure metal coatings, including Ni, Fe and Cr, on longterm oxidation kinetics, surface morphology and structure were studied. Ni-50Al
alloy and Ni-coated, Fe-coated and Cr-coated samples were pre-oxidized at 900 °C
in air. They were then oxidized isothermally at 1,000 °C in air. The bare Ni-50Al
alloy oxidized rapidly during the initial stage of oxidation due to the formation of
θ-Al2O3, but the oxidation rate decreased after α-Al2O3 had developed. Oxidationof the Ni-coated sample was slow from the beginning of oxidation even though the
θ-Al2O3 was predominated for a longer oxidation time. No θ-Al2O3 developed on
the Cr and Fe-coated samples, but the oxidation rates of these samples were much
faster than those of bare and Ni-coated samples. Cross-sectional images revealed
that the grain size of α-Al2O3, which formed on Cr and Fe-coated samples, wassmaller than those of bare and Ni-coated samples. These metal coatings affected
the microstructure of α-Al2O3 and they showed a strong effect on the growth rateof α-Al2O3 in the steady-state oxidation stage.
DOI 10.1007/s11085-014-9478-3

92

Prospect of Corrosion Resistive Aluminum Plating
Process on Magnesium Alloys
K. Azumi, M. Ueda and Y. Hang

J. Japan Inst. Light Metals, 64 15-20 (2014).

Fundamental aspect of plating process of Mg alloys from the view points ofcorrosion engineering is introduced. Weak corrosion resistivity of Mg alloys must
be considered not only in the practical use but also even in each step of platingprocess for corrosion protection coatings. For example, different electrochemical
activity of α- and β- phases in AZ91D Mg alloy induces non- uniform dissolution
on the surface of these phases and thus degrades the uniformity in the following
processes. Combination of acidic agents, hydrochloric acid which promotes
uniform but phase-dependent dissolution and hydrofluoric acid which promotes
formation of insoluble Mg fluoride layer, can mitigate non- uniform dissolution ofα- and β- phases. Phase dependent non-uniform metal deposition also progresseson α- and β- phase surfaces in zincating and main coating processes. Such nonuniformity is induced by the degradation of substrate surfaces during the process
and low activity, i.e., inefficient charge transfer, for metal deposition reaction.
Protection and activation of the substrate surface are effective strategy to overcome
such difficulties. Predeposition of Cu nanoparticles on the substrate prior to thedeposition processes could improve considerably the uniformity, adhesivity andprotection ability of deposits due to induction of high efficient charge transfer pathwith high density to the substrate surface resulting in high density nucleation ofdeposits.

93

Convection-dependent Hydrogen Permeation into a
Carbon Steel Sheet
K. Fushimi, M. Jin, T. Nakanishi, Y. Hasegawa, T. Kawano, M. Kimura
ECS Electrochem. Lett. 3 (2014) C21-C23.
The Devanathan-Stachurski electrochemical cell for measurement ofhydrogen-permeation into a steel sheet was extended to an electrolyte-flowing
design. Increase in flow rate of the entry cell induces increase in hydro genevolution current at the entry electrode but decrease in hydrogen-permeation
current at the hydrogen-exit electrode. Hydrogen-permeation is actualized by asinusoidal perturbation of the entry-flow rate. The hydrogen-permeation
response, i.e., phase shift of the detection current from the evolution current,
was proportional to the square root of flow rate frequency and was dependent on
sheet thickness. The sinusoidal perturbation of entry-flow rate is a new factor
influencing hydrogen-permeation into the sheet.
DOI: 1149/2.011406eel

94

Corrosion Behaviour of Ferrite and Austenite Phases on
Super Duplex Stainless Steel in a Modified Greendeath Solution
J.-S. Lee, K. Fushimi, T. Nakanishi, Y. Hasegawa, Y-.S. Park
Corros. Sci. 89 (2014) 111-117.
Corrosion behaviour of super duplex stainless steel (SDSS) in
acidic chloride solution was investigated electrochemically. Potentiostatic
polarisations of SDSS at −0.377 and −0.447 VSHE resulted in selective dissolutionof γ- and α-phases, respectively, and were utilized for fabricating single-phaseelectrodes. Potentiodynamic polarisation curve of SDSS could be calculated
from those of single-phase electrodes. The higher corrosion current density andless noble corrosion potential of α-phase characterised by galvanic connection
with γ-phase indicated that α- and γ-phases were functioned as the anode and thecathode, respectively, in the corrosion of SDSS.
DOI: 10.1016/j.corsci.2014.08.014

95

Growth and Degradation of Anodic Oxide Film on
Titaniumin Sulphuric Acid Observedby Ellipso-microscopy
K. Fushimi, K. Kurauchi, Y. Yamamoto, T. Nakanishi, Y. Hasegawa,
T.Ohtsuka
Electrochim. Acta 144 (2014) 56-63.
The surface of polycrystalline titanium polarised anodically in
0.05 mol dm−3 sulphuric acid was monitored using an ellipso-microscope.
During dynamic polarisation, a patch-like bright image was seen on an ellipsomicroscopic view, and the brightness and image changed with increase inpotential. The change in the brightness and image mainly corresponded to
growth of an anodic oxide film on the surface. An in situ monitoring using theellipso-microscope revealed that the film formation rate was dependent on the
crystallographic orientation of the substrate. Breakdown of the film induced ina solution containing bromide ions was also monitored using the microscope.
Prior to the pitting propagation, the surface was partially changed with flow of alarge anodic current. AES measurement revealed that the formation of bromooxide resulted in localised film degradation followed by pitting corrosion.
DOI: 10.1016/j.electacta.2014.08.082

96Grain-dependent Passivationof Iron in Sulfuric Acid Solution
Y. Takabatake, K. Fushimi, T. Nakanishi, Y. Hasegawa
J. Electrochem. Soc. 161 (2014) C594-C600.
Passive films formed on single grains of a polycrystalline pure ironsubstrate were investigated in 0.05 mol dm−3 sulfuric acid with a micro- capillarycell (MCC). Passivation behavior under the condition of potentiostatic
polarization was strongly dependent on the crystallographic orientation of thesubstrate surface. Electrochemical impedance spectroscopy revealed that the
charge transfer resistance of the passivated surface was determined by thesubstrate orientation. Galvanostatic reduction and XPS analysis of the surface
passivated using the MCC showed that the substrate orientation affected thechemical state of iron in the oxide. The results suggested that the aging of thepassive film formed on the iron substrate depended on its crystallographic
orientation due to the differences in surface energy of the substrate surface thathas a bcc lattice structure. It was concluded that the grain dependency on theelectric property of the passive film arose from the compositional differences ofthe oxide film.
DOI: 10.1149/2.0901414jes

97

The Corrosion Resistance and Passive Film
Compositions of 12% Cr and 15% Cr ODS Steels in Nitric
Acid MediaS. Ningshen, M. Sakairi, K. Suzuki and S. Ukai
Corrosion Science, 78, 322-334 (2014).
The passive film compositions and corrosion resistance of 12% Cr and
15% Cr oxide dispersion strengthened (ODS) steels in 3 M HNO 3 to 9 M HNO3
was evaluated. The potentiodynamic polarization plots exhibited a shift incorrosion potential, and higher passive current density with increasing HNO 3
concentrations. In 12% Cr ODS steel, high corrosion rate was observed in all HNO3
concentrations. However, low corrosion rate observed in 15% Cr ODS steel was
attributed to Al2O3 enrichment. The TEM analysis indicated a complex Y2Hf2O7
formation in 15% Cr ODS steel, and this may have a role in suppressing
intergranular corrosion attack.

98

The Surface Characterization and Corrosion Resistanceof 11% Cr Ferritic/Martensitic and 9-15% Cr ODS Steels
for Nuclear Fuel Reprocessing Application
S. Ningshena, M. Sakairi, K. Suzuki, and S. Ukai
Journal of Solid State Electrochemistry,18, 411-425 (2014)
In spent fuel nuclear reprocessing plant, nitric acid is the main medium
used in PUREX method. The passive film compositions and corrosion resistanceof 11 % Cr ferritic/martensitic and 9–15 % Cr oxide dispersion strengthened steels
in different nitric acid concentrations were studied. The open circuit potential isshifted toward more noble potential as the concentrations increased from 1 M
HNO3 to 9 M HNO3 in all the investigated alloy steels. The results of thepotentiodynamic polarization plots also exhibited a shift in corrosion potential as
the concentrations increased from 1 M to 9 M HNO3. This shift is undesirable
because of risk of overshooting the potential beyond passive region and may result
into transpassive corrosion. The X-ray photoelectron spectroscopy results of thepassive film analysis are com- posed mostly of Fe2O3, Cr2O3, and Y2O3, and thedepth profile of Fe and Cr concentrations vary depending upon the nitric acidconcentration. The surface morphology after the corrosion test does not showintergranular corrosion attack at the nitric acid concentrations studied. It is
desirable that materials for use in nitric acid service are resistant to such corrosion
induced degradation.

99

Effect of Metal Cations on Corrosion Behavior andSurface Film Structure of the A3003 Aluminum Alloy in
Model Tap Waters
K. Otani, M. Sakairi, R. Sasaki, A. Kaneko, Y. Seki, and D. Nagasawa
Journal of Solid State Electrochemistry, 18, 325-332 (2014)
The effect of the metal cations, Na+, K+, Ca2+, Mg2+, Zn2+, and Ni2+, on
the oxide film structure and morphology changes during long-term immersion
corrosion tests of aluminum alloy (A3003) in model tap waters was investigated by
X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy. The
effect of the metal cations on the corrosion behavior was also investigated withmass change and electrochemical tests. The hardness of the metal cations, X, basedon the hard and soft acids and bases (HSAB) concept was applied to explain theeffect of metal cations on the passive oxide film structure and corrosion resistance.
The mass change rate and corrosion current density decreased with increasing metal
cation hardness. The XPS results showed that hard metal cations like Zn2+ and Ni2+
were incorporated in the oxide films, while the four soft metal cations were notincor- porated in the oxide films. The results are in good agreement with thosewhich could be expected from the HSAB hardness of the metal cations.

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Evaluation of Metal Cation Effects on Galvanic Corrosion
Behavior of the A5052 Aluminum Alloy in Low Chloride
Ion Containing Solutions by Electrochemical Noise
Impedance
M. Sakairi, R. Sasaki, A. Kaneko, Y. Seki, and D. Nagasawa
Electrochimica Acta, 131, 123–129 (2014)
The effects of metal cations on the galvanic corrosion behavior of theA5052 aluminum alloy in low chloride ion containing solutions (tap water) were
examined by electrochemical noise impedance. The electrochemical noise
impedance and conductance were calculated by the power spectral density (PSD)of the galvanic current and potential. The oscillations in the galvanic current
correlate well with the oscillations in the potential. The total charge (summation ofgalvanic current) during galvanic corrosion tests was suppressed by the addition of
Ca2+, while it was increased with Mg2+ addition. Only a small effect on mean
impedance and conductance was observed in solutions with Cu2+ and Mg2+, while
addition of Ca2+ strongly influences both the mean impedance and conductance.
These results may be explained by the passive film structure changes due to themetal cations. The results obtained in this study indicate that metal cations play avery important role in the corrosion behavior of A5052 aluminum alloys in tap
water.

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Line Shaped Porous Type Anodic Oxide Film Formation
on Aluminumby Sf-MDC with Coated Pt Wire ElectrodeT. Yamaguchi and M. Sakairi
Journal of the Surface Finishing Society of Japan, 65, 385-390 (2014)
It is possible to form highly ordered porous type anodic oxide film byanodizing in acid solutions such as oxalic acid, phosphoric acid, and sulfuric acid,and both pore size and thickness are controlled by the anodizing condition.
Therefore, porous type anodic oxide films are widely used and studied. However,almost all research on area-selected anodizing is carried out with mask-processes.
The solution flow type micro-droplet cell (Sf-MDC) has been applied to form thickporous type aluminum anodic oxide film locally. By coating a side wall Pt wire
electrode, it is possible to reduce the width of the formed anodic oxide line withoutchanges in the film formation reaction. Up to ten repeated passes, there is nochange in the oxide film growth rate; the width of the oxide lines was observed bya coated Sf-MDC electrode. (Japanese)102

Evaluation of Metal Cation Effects on Galvanic Corrosionof Aluminum Alloys in Low Chloride Ion Containing
Solutions with Electrochemical Noise
M. Sakairi, K. Otani, and R. Sasaki
Procedia Engineering, 86, 589-596 (2014),
The effect of metal cations on the galvanic corrosion behavior of A3003
aluminum alloy in low concentration of chloride ion containing solutions (tapwaters) was examined by electrochemical noise impedance. The electrochemicalnoise impedance and conductance were calculated by the power spectrum densityof the galvanic current and potential. The sum of the galvanic current during
galvanic corrosion tests was suppressed by the addition of Ca 2+, Zn2+ and Ni2+,
while it was increased with Mg2+ addition. These results may be explained by thepassive film structure changes due to the metal cations. The results obtained in thisstudy indicate that metal cations play an important role in the corrosion behaviorof A3003 aluminum alloys in tap water.

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Oxide Films on Nickel-base Alloys
in Water at 360 ˚C under PWR Environment
T. Ohtsuka, Y. Hamaguchi, M. Sakairi, K. Fushimi, K. Azumi, Y. Sakakibara,
and G. Nakayama
Proceedings of 16th International Congress Environmental Degradation ofMetals in Nuclear Power Systems (2014)
The oxide film on the nickel-base alloys exposed to the PWR
environment at 360°C in water containing 500 ppm B and 2.0 ppm Li was analyzed
by ellipsometry, Raman spectroscopy, IR-reflection absorption spectroscopy,
Auger electron spectroscopy, SEM, and laser scanning microscope. The oxide filmon the alloys consisted of the flat layer enriched by Cr oxide and the protuberance
particles enriched by Ni and Fe oxides. The number of the protuberance particles
was increased with the tensile stress added. The protuberance oxide particle wasassumed to emerge from the crack site of the flat oxide layer induced by the inner
stress in the oxide or by the tensile stress loaded from the outside.

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Electrochemical Noise Analysis on Modified 13%Cr
Stainless Steels in Sour Environments under Stress
M. Sakairi, J. Tatehara, Y. Mizukami, and S. Hashizume
Proceedings of EUROCORR2014, No. 7095 (2014)
Electrochemical noise analysis technique was applied to predict
initiation or propagation of pitting events, which is lead to SCC or SSC. It is also
try to clarify the relationship between features of PSD and initiation of crack or
pitting corrosion during immersion corrosion tests by using consecutive PSD
calculation technique. Consecutive average PSD can be calculated from rest
potential data, and the peaks of the average PSD shows good correlation with restpotential changes. The average PSD peaks enhances the rest-potential changes.
The enhancement by PSD make it possible to monitor initiation of localized
corrosion events in sour environments.

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Metal Cation Effects on Galvanic Corrosion Behavior of2024 Aluminum Alloy with Electrochemical Noise
M. Sakairi, A. Kaneko, and R. Sasaki
Proceedings of the Seventh China-Japan Seminar on Marine Corrosion andControl, 50-56 (2014)
The corrosion behavior of some aluminum alloys strongly depends on
the kinds of metal cations in the environments. However, only a few reports havefocused on the effect of metal cations on galvanic corrosion of aluminum alloys infresh or tap waters. In the present study, electrochemical noise analysis based
impedance technique was applied to evaluate the effect of metal cations on galvanic
corrosion of an aluminum alloys in model tap waters. The current fluctuations andpotential fluctuations showed good correlation. While, in Mg 2+ and Ca2+ added
solutions, no changes in potential and current were observed. The total charge(summation of the current density from 0 to 86.4 ks) changed with kind of metal
cation. These results clearly indicated that the galvanic corrosion rate was strongly
affected by the kind of metal cations.

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