Interface Vol. 23, No. 4, Winter 2014

VOL. 23, NO. 4 Winter 2014

Numerical Modeling for

CORROSION

IN THIS ISSUE 3 From the Editor:

Everybody Writes, Nobody Reads

7 From the President: ECS in Mexico

8

Cancun, Mexico: Meeting Highlights

20 Candidates for Society Office

31 Beyond Open Access 38 ECS Classics:

Sherlock Swann, Jr.: Electro-organic Chemist and Master Bibliographer

43 Tech Highlights 45 Numerical Modeling for Corrosion

47 The Use of Finite Element Methods (FEM) in the Modeling of Localized Corrosion

53 Obtaining Corrosion Rates

by Bayesian Estimation: Numerical Simulation Coupled with Data

59 Modeling Corrosion, Atom by Atom

65 Computer Simulation

of Pitting Corrosion of Stainless Steels

97 Phoenix, Arizona Call for Papers

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The Electrochemical Society Interface â&#x20AC;˘ Winter 2014

NEW

1

FROM THE EDITOR

Everybody Writes, Nobody Reads

I

am happy to report that people read Interface magazine. Just the other day I received a long letter commenting on the usefulness of the topical articles, this one specifically detailing the issue dealing with ionic liquids. The message of the letter was that the reviews in Interface are just as useful as the summary articles in peer-reviewed publications. Another reader, reacting to the side remark I made in my recent editorial about opening a dog kennel, wanted to unload his German shepherds on me. Yet another letter mentioned the Classics column and how nice it was to read recollections about scientists, written by other scientists and colleagues.

Interface does not have an officially gauged impact factor and we do not have a good measure of how well and thoroughly this magazine is read. Still, we like to hear that it is a useful medium for the members, the advertisers, and anybody else who may follow what shows up in our quarterly.

Publishing is a funny business. It was Michael Faraday, the spiritual mentor of all electrochemists, who once wrote this advice for scientific success: work, finish, publish.

There are, you see, two more parts to publishing and they precede the actual act of publishing.

The contemporary methods of success evaluation, the rubrics, as the assessment gurus like to call them, focus mostly on the documented last part of Faraday’s recipe for success. After all, unless the work is written up and others can read about it, it has little value. And published papers are so easy to count. Add to the count an impact factor multiplier and you have a straightforward assessment tool. The higher the impact factor of the journal, the higher the perceived quality of the article, and the higher A motivational sign above the author’s laboratory the rewards bestowed on the author door in DeKalb. once the activity reports are turned in.

And this also works in reverse, for an article in a no-impact factor publication, of which Interface is one, brings little joy to evaluators and little credit to the authors. Lucky are the few whose departments do not embrace the assessment rubrics, lucky are those who feel that they have enough papers in journals with high impact factors, and lucky us who get to read the well-written contributions to Interface by colleagues who care enough and volunteer their time and writing skills to us, without earning a publication with an impact factor in return.

May it be then a reward to all the Interface authors to know that there is a crowd of people who read their work. For each one receiving a comment from a happy reader, there is a number of happy readers who will not send a comment. So how much truth is in that “everybody writes and nobody reads” statement? The outward success indicator of Faraday’s advice is the “be published” part, which is somewhat recast onto the “publish or perish” mantra, for which the “nobody reads, everybody writes” is a wistful comment longing for the times when pressures to publish were perhaps lesser. Still, the need to publish is not a new phenomenon. The title statement is ascribed to the mathematician Pál Erdös, though this notion of state of affairs might have been circulating through science departments during his times fairly spontaneously without defined authorship. I heard it quite far back from my college instructor, who taught us the fine art of finding relevant literature in the volumes and stacks of Chemical Abstracts. Copiers were not accessible then, so an actual article was a precious commodity and it was thoroughly read and studied, and its ideas, properly referenced, were incorporated in our own work. And the statement “nobody reads, everybody writes” was then fully understood merely as a cynical statement, to be taken as a warning, not an instruction. To be understood the same way today, it probably needs to be followed by a colon, hyphen, and the letter J, i.e., :-J, a sidewise smiley face simulating a tongue in cheek and meaning irony.

Petr Vanýsek, Interface Co-Editor

Published by: The Electrochemical Society (ECS) 65 South Main Street Pennington, NJ 08534-2839, USA Tel 609.737.1902 Fax 609.737.2743 www.electrochem.org Co-Editors: Vijay Ramani, ramani@iit.edu; Petr Vanýsek, pvanysek@gmail.com Guest Editor: Shinji Fujimoto, fujimoto@mat.eng.osaka-u.ac.jp Contributing Editors: Donald Pile, donald.pile@gmail.com; Zoltan Nagy, nagyz@email.unc.edu Managing Editor: Annie Goedkoop, annie.goedkoop@electrochem.org Interface Production Manager: Dinia Agrawala, interface@electrochem.org Advertising Manager: Becca Compton, becca.compton@electrochem.org Advisory Board: Bor Yann Liaw (Battery), Sanna Virtanen (Corrosion), Durga Misra (Dielectric Science and Technology), Giovanni Zangari (Electrodeposition), Jerzy Ruzyllo (Electronics and Photonics), A. Manivannan (Energy Technology), Xiao-Dong Zhou (High Temperature Materials), John Staser (Industrial Electrochemistry and Electrochemical Engineering), Uwe Happek (Luminescence and Display Materials), Slava Rotkin (Nanocarbons), Jim Burgess (Organic and Biological Electrochemistry), Andrew C. Hillier (Physical and Analytical Electro-chemistry), Nick Wu (Sensor) Publisher: Mary Yess, mary.yess@electrochem.org Publications Subcommittee Chair: Krishnan Rajeshwar Society Officers: Paul Kohl, President; Daniel Scherson, Senior Vice-President; Krishnan Rajeshwar, 2nd VicePresident; Johna Leddy, 3rd Vice-President; Lili Deligianni, Secretary; E. Jennings Taylor, Treasurer; Roque J. Calvo, Executive Director Statements and opinions given in The Electrochemical Society Interface are those of the contributors, and ECS assumes no responsibility for them.

Authorization to photocopy any article for internal or personal use beyond the fair use provisions of the Copyright Act of 1976 is granted by The Electrochemical Society to libraries and other users registered with the Copyright Clearance Center (CCC). Copying for other than internal or personal use without express permission of ECS is prohibited. The CCC Code for The Electrochemical Society Interface is 1064-8208/92.

Canada Post: Publications Mail Agreement #40612608 Canada Returns to be sent to: Pitney Bowes International, P.O. Box 25542, London, ON N6C 6B2 ISSN : Print: 1064-8208

Online: 1944-8783

The Electrochemical Society Interface is published quarterly

by The Electrochemical Society (ECS), at 65 South Main Street, Pennington, NJ 08534-2839 USA. Subscription to members as part of membership service; subscription to nonmembers is available; see the ECS website. Single copies $10.00 to members; $19.00 to nonmembers. © Copyright 2014 by The Electrochemical Society. Periodicals postage paid at Pennington, New Jersey, and at additional mailing offices. POSTMASTER: Send address changes to The Electrochemical Society, 65 South Main Street, Pennington, NJ 08534-2839.

The Electrochemical Society is an educational, nonprofit 501(c)(3) organization with more than 8000 scientists and engineers in over 70 countries worldwide who hold individual membership. Founded in 1902, the Society has a long tradition in advancing the theory and practice of electrochemical and solid-state science by dissemination of information through its publications and international meetings.

The Electrochemical Society Interface • Winter 2014 All recycled paper. Printed in USA.

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Vol. 23, No. 4 Winter 2014

45 47

Numerical Modeling for Corrosion

by Shinji Fujimoto

Nobody Reads

The Use of Finite Element Methods (FEM) in the Modeling of Localized Corrosion

by C. Liu and R. G. Kelly

53

the Editor: 3 From Everybody Writes,

Obtaining Corrosion Rates by Bayesian Estimation: Numerical Simulation Coupled with Data

by Kenji Amaya, Naoki Yoneya, and Yuki Onishi

59

Modeling Corrosion, Atom by Atom

65

Computer Simulation of Pitting Corrosion of Stainless Steels

by Christopher D. Taylor

by N. J. Laycock, D. P. Krouse, S. C. Hendy, and D. E. Williams

the President: 7 From ECS in Mexico Mexico 8 Cancun, Joint International Meeting Highlights

18 Society News for 20 Candidates Society Office 36 People News Classics: 38 ECS Sherlock Swann, Jr.:

Electro-organic Chemist and Master Bibliographer

43 Tech Highlights 72 Section News 73 Awards 75 New Members 77 ECS Fellowship Reports 87 Student News Arizona 97 Phoenix, Call for Papers On the cover . . .

Adsorption geometries for chemisorbed layers of chloride ions and ammonia on iron surfaces, as simulated using density functional theory; see article on page 59.

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FROM T HE PRESIDENT

ECS in Mexico I

n October 2014, a joint international meeting between ECS and SMEQ was held in Cancun, Mexico.

The meeting was held at an interesting and efficient venue that provided the attendees with a rich technical program and even new opportunities. The meeting itself was co-sponsored by our partner society, Sociedad Mexicana de Electroquímica (SMEQ). We very much appreciated the efforts and hospitality of SMEQ President Facundo Almeraya Calderón and past presidents Norberto Casillas Santana and Yunny Meas. The interaction of the two societies provided larger and broader symposia, along with a chance to initiate new interactions.

The positive experiences from this second joint meeting of the two societies established a format for recurring meetings on a regular basis, probably every four years in Mexico. We hope it will be a platform for other societies in Latin America to join in this partnership with a regional flavor. Estoy deseando una relación larga y mutuamente beneficiosa. The reoccurring meetings format with regional partners follows our highly successful joint meetings with societies in Asia, which meet on a regular basis in Hawaii under the name PRiME. These partnerships promote international cooperation, education, and goodwill. I hope this relationship in the Western Hemisphere grows and engenders other opportunities in different parts of the world.

As reflected in the technical program in Cancun, the global interest in electrochemical and solid state science and technology has never been stronger. The Society’s technical areas are contemporary, including fundamental and applied topics such as energy, environmental issues, and electronics.

The meeting site was particularly friendly and efficient because the conference rooms were in closely-located buildings, making travel between sessions easy. The hotel package included all meals, enabling attendees to stay at the property’s restaurants, which promoted networking at all hours of the day. The unique flavor of the Mexican location was brought out in the Cena Baile at the end of the conference—¡un divertido fin a una semana productivo!

The Society’s initiatives and commitment to scholarly publications was reflected in awarding each attendee an Open Access article processing charge (APC) credit for publishing a peer-reviewed paper in the Society’s journals. By using this APC, a published paper in one of the Society’s journals will be an Open Access paper, and can be read worldwide without the need for the reader to have a subscription or single article charge. Open Access, as practiced by some publishers, may sacrifice quality or be very expensive. The ECS approach is purely for the benefit of authors and readers. It is the unrestricted distribution of the articles, which, because the papers receive the same, high-quality review and publication treatment, gives authors the widest possible distribution of their peer-reviewed, scholarly work, without sacrifice of prestige or quality. It makes the ECS journals the best place to publish high-quality, peer-

The Electrochemical Society Interface • Winter 2014

reviewed papers because publication occurs in a highly-cited, established journal and does not hold papers behind a paywall.

I hope everyone takes advantage of this unique opportunity.

There is a Society-wide commitment to support and fund this endeavor to publishing without barriers.

The Cancun meeting also had a new initiative—a facilitated brainstorming session that resulted in ECS awarding four unrestricted research grants, a program sponsored by the Bill & Melinda Gates Foundation. The topic was the application of electrochemical and solid state technology to address global sanitation and water challenges. The availability of clean water and secure sanitation is a significant challenge in the world and a major cause of disease and death. Plenary and brainstorming sessions were held early in the week to stimulate hallway discussions about the topic and allow meeting participants time to think about solutions to the presented problems. Attendees were invited to submit short proposals at the conference; by week’s end, ECS had awarded four unrestricted grants with the possibility of additional grants in the near future. This was the first time I experienced a focused outreach and funding event that happened (start to finish) at an international conference.

The keynote presentations were engaging and informative.

They were effective because the opening talks detailed many aspects of the sanitation and water problem not commonly known, and encouraged attendees to find innovative approaches to solving the problems. The presence of an informed and ready audience was a key aspect of the process. This approach opens new opportunities for other organizations to harvest the collective creativity and energy of a diverse group of scientists and engineers, just like those that attend ECS meetings. As a trial run, it was successful, and it is stimulating consideration for similar future events in other technical areas.

I have had the great fortune to participate in many publications and endeavors through ECS as Editor of Interface, the Journal of The Electrochemical Society and Electrochemical and SolidState Letters, and now as an officer of the Society. Along the way, I have had some of the most remarkable outcomes from chance meetings. The focus and topics in electrochemistry and solid state science have changed over the years but are stronger and more relevant than ever, as shown by the enthusiasm and breadth in Cancun. This may be my last column in an ECS publication, so I want to say a special word of thanks to all those who work or volunteer for ECS. It is a great organization to be associated with. I would also like to give a few words to those involved in the Cancun meeting—¡Gracias a todos los participantes en esta conferencia!

Paul A. Kohl ECS President

7

CANCUN

Mexico October 5-9, 2014 Moon Palace Resort

Highlights from the Joint International ECS and SMEQ Meeting in Cancun

T

his was a joint international meeting organized by ECS and SMEQ (La Sociedad Mexicana de Electroquímica). This was the second meeting at the Moon Palace all-inclusive resort; the first was in 2006. At the meeting there were 2,299 presentations given in 51 symposia with attendance of over 2,100 participants.

Plenary Session On Sunday evening Noberto Casillas, former President of Sociedad Mexicana de Electroquímica, welcomed everyone on behalf of SMEQ and ECS, and opened the meeting. He noted that over 2,100 attendees were on hand for this meeting, which was the 226th meeting for ECS, the 7th meeting for ECS Mexico Section, and the 29th congreso for SMEQ. ESC President Paul Kohl also welcomed the audience and presided over the awards presentations, which included 10 different awards with 41 winners.

The Plenary Lecture was given by Victor Gerardo Carreón Rodrígues and the title of his presentation was Advances in Science, Technology, and Innovation (STI) in Mexico. Dr. Rodríquez is the Deputy Director of Planning and International Cooperation (Planeación y Cooperación Internacional) a unit of CONACYT (the Mexico National Council for Science and Technology). He explained how Mexico's goal is to develop the capabilities to transition toward a knowledge-based society and economy by growing the national investment in science, technology, and innovation; developing and strengthening highly qualified human resources; strengthening regional development; promoting exchange between academic research and the economic sector; strengthening scientific and technological infrastructure; and strengthening the STI capacities in biotechnology.

Former SMEQ President Noberto Casillas, (left) presented a plaque to Victor Gerardo Carreón Rodrígues (right) for giving the Plenary Lecture.

SMEQ and ECS leadership at the plenary session: (left to right) Facundo Almeraya Calderón, SMEQ President; Paul Kohl, ECS President; and Noberto Casillas former SMEQ President.

8

The Electrochemical Society Interface • Winter 2014

226th Meeting of The Electrochemical Society XXIX Congreso de la Sociedad Mexicana de Electroquímica th 7 Meeting of the Mexico Section of The Electrochemical Society

SOCIE T Y NE WS

2014 ECS and SMEQ Joint International Meeting

Ralph Brodd (third from left) at the special reception in his honor for winning the Edward Goodrich Acheson Award. Standing with Dr. Brodd are (left to right): Richard Alkire, Dorothy Brodd, (Dr. Brodd), Hariklia Deligianni, Sol Krongelb, and Lubomyr Romankiw.

Awards Highlights The Edward Goodrich Acheson Award was established for distinguished contributions to the advancement of any of the objectives, purposes, or activities of ECS. This year the award went to Ralph Brodd, President of Broddarp. Dr. Brodd is an ECS Past President and an ECS Honorary Member. Dr. Brodd was honored for his exceptional service to the Society, and for inspiring leadership in innovation, commercialization, management, and public service activities related to battery science.

This year the winner of the Charles W. Tobias Young Investigator Award was Adam Weber, a staff scientist at the Lawrence Berkeley National Laboratory. He received the award for his research leadership that furthered the understanding of transport phenomena in electrochemical systems through the use of mathematical modeling and advanced diagnostic techniques. Dr. Weber presented his award address entitled “Understanding Transport Phenomena in PolymerElectrolyte Fuel Cells” at the meeting. The Charles W. Tobias Young Investigator Award is given to a young scientist or engineer who has produced outstanding engineering work or scientific in fundamental (continued on next page) The Electrochemical Society Interface • Winter 2014

Adam Weber (left) received the Charles W. Tobias Young Investigator Award from ECS President Paul Kohl (right).

9

Cancun Meeting Highlights (continued from previous page)

ECS President Paul Kohl (center, back row) inducted the 2014 Class of ECS Fellows. Seated in the front row holding their plaques (from left to right) are Fred Roozeboom, Bruce Parkinson, Jose H. Zagal, Gerardine Botte, Piotr Zelenay, Alvin Salkind, and Jay W. Grate. Standing in the back row without their plaques (from left to right) are Yasuhiro Fukunaka, Tooru Tsuru, (President Kohl), Michael M. Thackeray, and George Blomgren. Missing from the photo are Ralph J. Brodd, Dirk M. Guldi, Sudipta Seal, and Harry L. Tuller. (continued from previous page)

ECS President Paul Kohl (right) presents the Norman Hackerman Young Author Award to Rahul Malik (center), while his co-author and co-award winner Aziz Abdellahi (left) waits to receive his award.

10

or applied electrochemistry or solid state science and technology. The award is named in memory of Charles Tobias, the 69th ECS President, who is considered the “father” of electrochemical engineering.

The Norman Hackerman Young Author Award for the best paper published in the Journal of The Electrochemical Society in the field of electrochemical science and technology went to Rahul Malik and Aziz Abdellahi, for their paper, “A Critical Review of the Li Insertion Mechanisms in LiFePO4 Electrodes.” (JES, Vol. 160, No. 5, p. A3179) The Bruce Deal and Andy Grove Young Author Award, an award newly established in 2013, was presented to acknowledge the best paper published in the ECS Journal of Solid State Science and Technology, for a topic in the field of solid state science and technology by a young author.

Konstantino Spyrou was the recipient of this award for his paper, “Hydrogen Storage in Graphene-Based Materials: Efforts Towards Enhanced Hydrogen Absorption.” (JSS, Vol. 2, No. 10, p.

M3160) The Electrochemical Society Interface • Winter 2014

2014 Electrochemical Energy Summit The 2014 Electrochemical Energy Summit took place in Cancun and presented attendees with the “Science for Solving Society’s Problems Challenge.” The multi-day workshop addressed critical technology gaps and water, sanitation, and hygiene challenges in partnership with the Bill & Melinda Gates Foundation. The workshop was designed to foster collaborative problem solving among participants and apply the collective brainpower of the joint ECS and SMEQ meeting attendees to complex technical challenges that required integrated thinking and out-of-the-box solutions.

The workshop began on Monday morning with opening remarks and brief presentations of the issues and priorities, and was followed by a question and answer session. Later that day, the participants were guided through facilitated brainstorming and working group sessions.

The first day culminated with a summary of the brainstorming session and a solicitation for proposals. After the first day, the researchers had two days to develop their one-page pitch. On Thursday the chosen applicants gave short presentations to the panel of judges.

The workshop wrapped up on Friday with the announcement of the winners. (See related article on page 18 in this issue of Interface.)

The following were members of the Steering Committee for this event: Luis Gerardo Arriaga, Centro de Investigación y Desarrollo Tecnologico en Electroquímica; Kathy Ayers, Proton OnSite; Roque Calvo, ECS Executive Director; Dan Fatton, ECS Director of Development and Membership Services; Carl Hensman, Bill & Melinda Gates Foundation; Paul Kohl, Georgia Tech and President of ECS; Paul Natishan, Naval Research Laboratory and Past President of ECS; Brandy Salmon, RTI International; Brian Stoner, RTI International; E. Jennings Taylor, Faraday Technology, Inc. and Treasurer of ECS; and Eric Wachsman, University of Maryland, Energy Research Center.

2014

2013

ECS President Paul Kohl (right) presented an ECS Service Award to Tetsuya Osaka for his outstanding contributions as ECS President during his 2013-2014 term.

ECS was pleased to bring back the ever-popular Sunday Evening Get-Together. The photo above shows attendees enjoying themselves at the event held outside at the Moon Palace, with the Caribbean as a backdrop.

The Electrochemical Society Interface • Winter 2014

11

Cancun Meeting Highlights (continued from previous page)

On Monday night, more than 140 students attended a special invitation-only Student Mixer to relax and compare notes with their peers. The mixer was possible thanks to the generous support of Gelest.

On Wednesday, the sun rose at 6:40 a.m., but many were already up before dawn. Some tried to get a glimpse of the lunar eclipse, some were readying for early business meetings, and a group of enthusiasts assembled for the second ECS Free the Scienceâ&#x201E;˘ 5K Run. (The first one took place six months earlier, in Orlando). Matthew Lawder (men) and Rana Mohtadi (women) won the race. For Matthew it was his second win at the ECS run, and he plans to win again at the Chicago meeting in the spring and takes on all challengers. Proceeds from this event are used to benefit the ECS Publications Endowment.

12

The Electrochemical Society Interface â&#x20AC;˘ Winter 2014

As part of the career development series, ECS presented a Panel of Professionals on Monday, October 6. Attendees heard from three guest speakers, representing industry, academia, and government, each discussing the unique challenges and opportunities of pursuing a career in their chosen field. The panel was moderated by Jamie NoĂŤl (University of Western Ontario). The speakers, pictured above (left to right), were Luis Garfias (Wood Group Kenny), Elizabeth Podlaha Murphy (Northeastern University), and Rudy Buchheit (The Ohio State University).

Travel Awards All Divisions and some topical symposia support travel grants, most of which are directed to students giving presentations at ECS meetings. The following students and young professionals received either a registration waiver and/or travel support to attend the Cancun meeting; or received a Divisional or symposium sponsored at-meeting poster award: Diana Morales Acosta, Andrei Akbasheu, Lik Ming Aw, Sriya Banerjee, Shuyu Bao, Elodie Beche, Michael Clark, Baratunde Cola, Kely EscorciaRojas, Maria Escudero-Escribano, Xin Fang, Eleanor Gillette, Paul Gondcharton, Colin Gore, Charlie Gosse, Rolf Grieseler, John Hart, Ramsey Hazbun, Chen-Pin Hsu, Yilin Huang, Sijia Jiang, Jr-Jian Ke, Yun-Hyuk Ko, Volker Kurz, Donghoon Kwon, Du-Yeong Lee, Robert Lillard, Fa-Sain Lo, Raciel Lopez, Xinyu Lu, Natalia Macauley, Damien Massy, Angela Mohanty, Tarun Mudgal, , Christopher Pellegrinelli, Joseph Rheinhardt, David Richardson, Marcel Rost, Ashley Ruth, Biplab Sarkar, Robert Spotnitz, Bharatkumar Suthar, Esther Takeuchi, Jianshi Tang, Gregory Timp, Tzu-Chiao Wei, Michael Workman, Ming Wu, Lu Yu, Yang Yu, and Yuanyuan Zhang.

Find out how you can get a travel grant to your next meeting:

electrochem.org/travel_grant

The Electrochemical Society Interface â&#x20AC;˘ Winter 2014

13

Cancun Meeting Highlights (continued from previous page)

Energy Summit Sessions

14

The Electrochemical Society Interface â&#x20AC;˘ Winter 2014

Scenes from the Exhibit Floor and Poster Sessions

The Electrochemical Society Interface â&#x20AC;˘ Winter 2014

15

Cancun Meeting Highlights (continued from previous page)

The Table Tennis Challenge

ECS President Paul Kohl challenged the leadership of SMEQ to a ping-pong match. SMEQ was represented by its former president, Noberto Casillas. A hard match was played, but in the end ECS won and was awarded the trophy. The photo above at left shows Noberto Casillas (left) and Paul Kohl (right) during the action. The photo on the right shows the two contestants with Cole Gilmore, Paul Kohlâ&#x20AC;&#x2122;s grandson.

A festive and gallant dinner and dance party is a nice way to conclude an event. In Cancun, it was the Cena Baile, arranged on Thursday evening, before the guests departed on Friday. The dance party was set on a terrace facing the sea. A live band entertained the guests at this special event.

16

The Electrochemical Society Interface â&#x20AC;˘ Winter 2014

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VOL. 23, NO. 2 Summer 2014

IN THIS ISSUE 3 From the Editor:

Working With Stuff

9 From the President:

The Grandest Challenge of Them All

11 Orlando, Florida

ECS Meeting Highlights

36 ECS Classics–

Hall and Héroult and the Discovery of Aluminum Electrolysis

39 Tech Highlights 41 Twenty-Five Years of

Scanning Electrochemical Microscopy

43 Studying Electrocatalytic

Activity Using Scanning Electrochemical Microscopy

47 Measuring Ions with

Scanning Ion Conductance Microscopy

www.electrochem.org

VOL. 23, NO. 2

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If you haven’t visited the ECS Digital Library recently, please do so today!

25 Years of Scanning Electrochemical Microscopy

53 Electrochemistry at the Nanoscale: The Force Dimension

61 Functional Electron

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SOCIE T Y NE WS

ECS Seeds Four Projects Aimed at Solving the World’s Sanitation Challenges

by Dan Fatton ECS awarded $210,000 of seed funding to four innovative research projects addressing critical technology gaps in water, sanitation, and hygiene being faced around the world.

In its first “Science for Solving Society’s Problems Challenge,” ECS partnered with the Bill & Melinda Gates Foundation to leverage the brainpower of the many scientists in electrochemistry and solid state science and technology that regularly attend ECS meetings.

The four grantees were identified during a multi-day workshop at the Electrochemical Energy Summit in Cancun, Mexico held October 5-9, 2014.

Over 100 researchers were guided through a brainstorming and working group session with the theme of improving access to clean water and sanitation in developing countries. Brandy Salmon, PhD, Senior Innovation Advisor from RTI International, facilitated the brainstorming. “The idea was to inspire researchers to consider the many ways electrochemistry can be applied to solve issues of global significance,” explained Salmon. “ECS provided a lab for collaboration that generated new ideas and partnerships.”

Ideas suggested ran the gamut from turning urine to hydrogen power and using microorganisms that harvest energy from marine sediments to looking at “molecular slip” as part of making waste pipes more efficient. A summary of the brainstorming session is available for download on the ECS website. The format provided a unique opportunity for researchers to generate possible solutions and then almost immediately start testing them.

After the brainstorming session, researchers had two days to develop a one-page proposal. Thirty finalists were selected from the 47 proposals submitted. Those 30 were given five minutes each in the “Shark Tank” to present their ideas to a panel of judges followed by five minutes of questions. The funding review panel scored proposals for innovation, collaboration, mission, and capacity. The final deliberations and selection concluded the next day.

“This really is science for solving society’s problems,” noted Paul Kohl, ECS President. “An expert, in this case the Bill & Melinda Gates Foundation, presents the problem, ECS gathers ideas from the brightest minds in the field, and their peers review the proposals and grant the money in a very short period of time. No red tape. More time will be spent on addressing the problem and less time on raising money to perform the research.”

“This is true reality programing, a model for moving the needle on real-world problems,” said Roque Calvo, ECS Executive Director.

“We would like to replicate this at our future biannual meetings, which regularly attract more than 2,000 of the brightest minds in science. We have invaluable assets in our membership; we just need corporations and foundations to identify the challenges they’d like to address, and provide the capital so our membership can start tackling these additional challenges.”

Winners of the First “Science for Solving Society’s Problems Challenge” • Artificial Biofilms for Sanitary/Hygienic Interface Technologies (A-Bio SHIT) Plamen Atanassov, University of New Mexico, $70,000 Interfaces: Produce biocatalytic septic cleaning materials that incorporate microorganisms removing organic and inorganic contaminants, while simultaneously creating electricity (or hydrocarbon fuel) for energy generation in support of a sustainable and portable system.

• In situ Electrochemical Generation of the Fenton Reagent for Wastewater Treatment Luis Godínez, Centro de Investigación y Desarrollo Tecnológico en Electroquímica SC, Mexico, $50,000 Disinfection: Study the electro-Fenton approach using activated carbon to efficiently oxidize most of the organic and biological materials present in sanitary wastewater so that recycling of the wastewater might be possible.

• powerPAD Neus Sabaté, Institut de Microelectrónica de Barcelona (CSIC); Juan Pablo Esquivel, University of Washington; and Erik Kjeang, Simon Fraser University, $50,000 Monitoring and Measurement: Develop a non-toxic portable source of power for water measuring and monitoring systems, which will not require recycling facilities. Using inexpensive materials such as paper, nanoporous carbon electrodes, and organic redox species, the team will strive to create a biodegradable and even compostable power source.

• More than MERe microbes: Microbial Electrochemical Reactors for water reuse in Africa Gemma Reguera, Michigan State University, $40,000 Chemical Conversion: Develop microbial electrochemical reactors that harvest energy from human waste substrates using bioanodes engineered to process the waste into biofuels while simultaneously cleaning water for reuse. The microbial catalysts will be selected for their efficiency at processing the wastes, but also for their versatility to process other residential and agricultural waste substrates. This will provide an affordable, easy to operate system for the decentralized processing of a wide range of wastes for improved sanitation, water reuse, and energy independence.

Noé Arjona, of Centro de Investigación y Desarrollo Technológico en Electroquímica, participates in the workshop at the Electrochemical Energy Summit.

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Eric Wachsman, a member of the Steering Committee for the 2014 Electrochemical Energy Summit.

Senior Technology Integration and Innovation Manager from RTI International, Brandy Salmon, supported the development of workshop resources, and provided structure and guidance for the workshop. Dr. Salmon is among a team of Innovation Advisors at RTI who provide innovation management and strategy, technology commercialization, assessment, and partnership support for federal agencies, universities, foundations, and companies. Dr. Salmon is an experienced facilitator and expert in innovation management and technology assessment.

Dan Fatton is the Director of Development and Membership Services for ECS and adds the following comments: I’ve been working with ECS for less than 2 years, and implementing programs like this has been one of the best, most rewarding parts of my job. We are very excited about the four grantees that ECS selected

Clement Cid, of the California Institute of Technology, gives a morning talk at the workshop.

in Cancun, but I’m also energized by the innovative experiment we’ve just undertaken. ECS is already considering future opportunities for the “Science Solving Society’s Problems” program, but if you have an idea for a similar problem solving collaboration, or want to share some other new approach that ECS should consider for our meetings, members or something else, let’s talk. Please email me at dan.fatton@ electrochem.org.

ECS Future Meetings 227th Meeting Chicago, IL

May 24-28, 2015 Hilton Chicago

CHICAGO ECS Conference on Electrochemical Energy Conversion & Storage with SOFC-XIV Glasgow, Scotland

228th Meeting Phoenix, AZ

October 11-16, 2015 Hyatt Regency Phoenix & Phoenix Convention Center

July 26-31, 2015 Scottish Exhibition and Conference Center

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229th Meeting

San Diego, CA

May 29-June 3, 2016 Hilton San Diego Bayfront & San Diego Convention Center

PRiME 2016

Honolulu, HI

October 9-14, 2016 Hawaii Convention Center & Hilton Hawaiian Village

Go to electrochem.org/meetings for the latest information.

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CA NDIDAT ES FOR SOCIE T Y OFFICE The following are biographical sketches and candidacy statements of the nominated candidates for the annual election of officers for ECS. Ballots (and instructions for voting either online or by mail) will be sent in January 2015 to all Voting Members of the Society. The offices not affected by this election are that of the Treasurer and the Secretary.

Candidate for President

Candidates for Vice-President

Daniel A. Scherson is currently the Frank Hovorka Professor of Chemistry at Case Western Reserve University.

He received a PhD in chemistry from The Universit y of California at Davis under the late Joel Keizer working in the area of nonlinear, non-equilibrium thermodynamics. His interests in interfacial science prompted him to spend the next four years as a postdoctoral research associate in the laboratories of John Newman at UC Berkeley, Phil Ross at the Lawrence Berkeley Laboratory, Ernest B. Yeager at Case Western Reserve University, and finally at the Fritz Haber Institute in Berlin, Germany, working both with Heinz Gerischer and Dieter Kolb, from whom he acquired both theoretical and experimental knowledge in the general area of physical electrochemistry, which ultimately shaped his academic career.

In 1983, he joined the Chemistry faculty at Case Western Reserve University, where he is currently Director of The Ernest B. Yeager Center for Electrochemical Sciences. His research interests include the development and implementation of linear and nonlinear spectroscopic and structural techniques for the in situ monitoring of interfacial electrochemical events, including operating devices, such as fuel cells, batteries, and electrosynthetic reactors. Daniel Scherson has over 240 journal publications, seven U.S. patents, and hundreds of conference presentations.

He has been a member of ECS since 1976.

He received a number of prestigious awards, including the IBM Faculty Development Award, David C. Grahame Award of the Physical Electrochemistry Division of ECS, The Faraday Medal of the Electrochemistry Groups of the Royal Chemical Society, The Japan Society for the Promotion of Science Fellowship, the Alexander von Humboldt Senior Fellowship Award, and the Vittorio de Nora-Diamond Shamrock Postdoctoral Fellowship. He has also served as Chair of the Physical Electrochemistry and of the Battery Divisions of ECS and is a

Yue Kuo is a Dow Professor in chemical engineering with a joint appointment in electrical engineering and materials science and engineering at Texas A&M University.

He received a Doctor of Engineering Science from Columbia University in 1979.

He subsequently did industrial R&D including IBM’s T. J. Watson Research Center and Silicon Valley. He established the Thin Film Nano & Microelectronics Research Laboratory in 1998 at Texas A&M University. In his early career, Dr. Kuo performed work on batteries, electrophoresis, and more. Dr. Kuo has pioneered works on large area PECVD, RIE, as well as TFT materials, devices, fabrication processes, and new applications, which have resulted in breakthroughs and major impacts to worldwide productions. His IC research is focused on device physics, reliability, Cu interconnects, doped metal oxide high-k gate dielectric, nonvolatile memories, and novel LEDs. Dr. Kuo has authored over 400 papers and edited 2 TFT textbooks, 3 books of lectures, journals, and 27 proceedings volumes. Honors include ECS Fellow, IEEE Fellow, ECS EPD award, distinguished research and innovation awards, 10 IBM awards, honorary professorships, 150 plenary/ keynote/invited speeches, 11 patents, and best paper awards. Dr. Kuo has served on advisory and review boards and panels for U.S. national academies, industry, universities, and governments globally.

Dr. Kuo’s first contact with ECS was in 1974 as a reader of the Journal of The Electrochemical Society (JES) during his work on batteries. He started attending ECS conferences in 1987 and became an active member in 1989. He served as an associate editor of JES and Electrochemical and Solid-State Letters (2003–2012) and a technical editor of ECS Journal of Solid State Science and Technology and ECS Solid State Letters (2012–present). He served EPD as an executive committee member (1995–present), chair of award committee (2003-2005), vice-chair (2000–2004,

Joe Stetter has been an active member of ECS for almost 40 years. Dr. Stetter joined the NYC Section in 1975 and attended local meetings at the Stevens Institute of Technology in Hoboken, NJ. In 1980 Dr. Stetter moved to the Chicagoland Area (Argonne National Laboratory) and reinvigorated the ECS Chicago Section while being a professor and leading a large electrochemistry group at the Illinois Institute of Technology, Chicago. Now residing in the San Francisco Bay area, Dr. Stetter continues to actively participate in ECS as a presenter, symposium organizer, and committee worker.

Over the years Dr. Stetter have served ECS in many capacities, such as, secretary, treasurer, chair and past chair of the Sensor Division; Technical Affairs Committee; Education Committee; chair of the Individual Membership Committee; Honors and Awards Committee; and Adviser to the Battery and other Divisions. Furthermore, Dr. Stetter has been published in ECS journals, edited and reviewed for ECS journals, given short courses, and organized and chaired national and international symposia. These include chairing the 2001 International Meeting on Electronic Noses and Olfaction as part of the ECS meeting in Washington DC, Solid State Devices III (2002), Nanostructured Thin Films (2003), Sensors, Actuators and Microsystems (2003), Electrophoresis and Microfluidics (2004), Carbon Nanotubes and Nanostructures (2005), Clinical and Diagnostic Sensors and Systems (2006), Sensors Arrays and Multi-Dimensional Sensor Systems (2006), and many more to the present.

Dr. Stetter’s current work is focused on the commercialization of electrochemical sensor technology. He is currently President and CTO of KWJ Engineering Inc, and a startup company, SPEC-Sensors LLC, which is his fourth successfully owned and operated company. Dr. Stetter remains active in academia, as well, with productive collaborations at Oakland University, Wisconsin Lutheran College, UC Berkeley,

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Daniel A. Scherson (continued from previous page)

Fellow of ECS. He has held the positions of Associate Editor (1997-2007) and Editor of the Journal of The Electrochemical Society (2008-2012).

Yue Kuo (continued from previous page)

2007- 2008), and chair. He served in ECS’s solid state award committee (2004-2006) and nanotechnology committee (2003-2004) as well as on its Board of Directors (20092011). He taught ECS short courses (1994 and 1996), and organized and chaired many symposia. He founded the world’s longest continuously held ECS TFT symposium series (of 24 years) with the publication of 12 proceedings volumes. He represented ECS in the SEMI/ECS CSTIC conference (2010-present). He has been instrumental in promoting ECS in many countries.

Statement of Candidacy In the past century, ECS has achieved its goals of advancing electrochemistry, solid state science, and allied subjects through encouraging research, dissemination of knowledge, and education of members.

In order to remain vibrant and relevant, ECS has to grow continuously and respond quickly to the changing technical needs and interests of its members.

The ECS membership can be increased to offer additional member services. By joining ECS, scientists and engineers in emerging countries can gain updated knowledge and international experience.

Engineers in developed countries can be prepared for professional advancement and students can obtain access to top-quality publications and be exposed to scientific and professional atmospheres. Existing ECS members can be encouraged to participate in committees and conference organization to shape the future of ECS. Recognition of members for meeting outstanding scientific achievements and for sustained services to ECS could be expanded.

The biannual ECS meetings have successfully attracted thousands of attendees to present papers, join committee meetings, and communicate with colleagues or technical experts. More emerging topics can be included in the program to benefit existing members and to attract new members. In order to expand the impact to the scientific community,

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ECS can: (1) co-sponsor more meetings with societies that have complementary interests; and (2) sponsor or co-sponsor small-size conferences focused on specific subjects. More industry and government experts can be invited to deliver talks on general topics of interest to members.

The excellent reputation the ECS enjoys is maintained by the high-quality of its journals, ECS Transactions, and Interface, through joint efforts of authors, editors, and staff. In order to face the vigorous competition of the electronic age, continuous improvements in manuscript quality, impact factors, and the peer-review process are required. More original or high-impact results could be included in these publications through mechanisms of recruiting authors and market promotion.

The timely publication of more focused issues on emerging topics is also very helpful.

ECS offers short courses on scientific and career-enhancement topics at international meetings to benefit members.

The program can be expanded, for example, by offering more new or fundamental courses. Mini-courses can be offered by organizing several invited speakers in different but related symposia; this can be archived electronically and be available to ECS members after the proper intellectual property clearance.

It is an honor and privilege to serve ECS. If elected, I plan to continue my efforts in promoting the Society programs that benefit members and science.

Joe Stetter (continued from previous page)

and as a Visiting Scholar in Mechanical Engineering at Georgia Institute of Technology in Atlanta, GA. His expansive experience in leading science, technology, business, scholarship, and mentorship, has allowed for successful commercialization of electrochemical technology and many product lines still in use today to protect human health.

Statement of Candidacy This is the most important part of my statement. The ECS is a prestigious and powerful driving force for electrochemistry and science and engineering in general.

The meetings are an excellent size for substantive exchanges of scientific ideas.

A great vitality in this activity is possible by incorporating many young minds mixed

with the guidance and the wisdom of our senior members coupled to the ECS history and experience. I would like to place a high priority on attracting and involving young researchers into our society’s activities, and this includes meetings, publications, presentations, and governance. Resources are always limited and ECS can benefit from increased involvement with other like-minded societies and industrial sponsorships.

I have always been a team builder in my companies and understand the importance and the power of multifaceted teams. Starting with our existing strong academic, industry, business, and government collaborations, we can strengthen associations and add new ones that fit the model of our existing successful ones. We can accomplish a great deal by leveraging our senior membership and their relationships within the field as well as tapping into those that I have developed over the years.

Of course it is important to maintain and strengthen the existing infrastructure at ECS including our publications by promoting the distinct qualities (like our not-for-profit approach) and raising the impact factor (the relevance of this is changing in our world but still important). Greater impact comes from addressing, with focus, the most important societal challenges: health, energy, food, water, and resource management with our electrochemistry knowledge and broader integration thereof.

I have to say that I consider much of the ECS leadership and the membership is very strong today and I have great respect for those who have been guiding and contributing to our activities. In this regard, I can only say that I will bring my unique resources, experience, and contacts to the ECS senior management to carry the best of our activities forward. My mission is to advance electrochemistry science and engineering, preserve our integrity and high standards, and lend my efforts to increase revenue and the prestige of our society for the benefit of our growing membership. This will allow the ECS to continue to be relevant and important to a strong world scientific community.

Having experience in academia, publishing, grantsmanship, company startups, raising funds, management, and business, as well as extensive involvement in ECS and its operations, makes me qualified to contribute as Vice-President. I would be honored to serve the Society and you, its members, in this capacity. Thank you for your consideration of my candidacy.

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ECS Appoints New Technical Editor

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he Electrochemical Society is pleased to announce the appointment of Doron Aurbach as the next Technical Editor of the Batteries and Energy Storage technical interest area for the Journal of The Electrochemical Society (JES) and ECS Electrochemistry Letters (EEL).

Doron Aurbach is a full professor in the Department of Chemistry, leads an electrochemistry group of 40 people, and is a Senate member at Bar-Ilan University (BIU).

He chaired the Department of Chemistry during 2001-2005. Prof. Aurbach founded the electrochemistry group at BIU 28 years ago. Since then over 40 PhD and 60 MSc students have worked with Prof. Aurbach to earn their degrees. His team studies the electrochemistry of active metals, non-aqueous electrochemical systems, electrochemical intercalation processes, electrochemical water desalination, and electronically conducting redox polymers. He also develops spectroscopic methods (in situ and ex situ) for sensitive electrochemical systems, and develops rechargeable high energy density batteries and EDL capacitors. Prof.

Aurbach collaborates with several academic groups throughout the world and with a number of leading industries in Israel and elsewhere (e.g., BASF Germany and GM USA).

Prof. Aurbach has published more than 470 peer reviewed papers (nearly 19,000 citations with an H index of 69), 21 patents, 19 chapters in books, and presented his scientific work in hundreds of invited talks in international conferences. Prof. Aurbach served as an associate editor in 4 electrochemistry journals: the aforementioned JES and EEL, and Electrochemical and Solid-State Letters (journals of The Electrochemical Society); and Journal of Solid State Electrochemistry (Springer). He is a fellow of the ECS

(2008), ISE (2010) and MRS (2012). He is the head of the Israel National Research Center for Electrochemical Propulsion (founded in 2012) and the chairman of the Israeli National Authority for Laboratory Accreditation (since 2010). He has received numerous awards including: the ECS Battery Division Technology Award (2005); the Israel Vacuum Society (IVS) and Israel Chemical Society (ICS) Excellence Prizes (2007, 2012); the Landau Prize for Research towards Green Energy (2011); the ECS Battery Division Research Award; the Kolthoff Prize (2013); and the E. B. Yeager prize of the International Battery Association (2014). With his nomination as the Technical Editor for the Batteries and Energy Storage area of the ECS journals, Aurbach conveys the following massage: “The Electrochemical Society attracts prominent scientists, young researchers, students, industrial partners, and academic institutions from all over the world having interests in electrochemistry, materials science, and surface science. The ECS journals serves this community by fulfilling a central role in the publication of highly valuable and solid scientific information in all the fields that the ECS represents.

The ECS publications over the years have been supported by a very dedicated and professional editorial board that provides the best routes for publishing promptly high quality papers, and it intends to continue this tradition. The editorial board of ECS is committed to provide authors the best service in terms of highly effective, qualified, fair and prompt reviewing processes and then, a very quick publication procedure.”

Robert F. Savinell, editor of the Journal of The Electrochemical Society and ECS Electrochemistry Letters said, “We are pleased to welcome Prof. Aurbach to this leadership role with the ECS journals.

He brings extensive experience, depth of understanding of the field, and great energy to the editorial board. We look forward to his help in making the ECS journals ‘the journals of choice’ for authors in the electrochemical and related fields.”

ECS Welcomes New Staff Member T

im Gamberzky joined ECS in November of 2013 and in his capacity as Chief Operating Officer has contributed to the advancement of the Society through his efforts to improve our efficiency and effectiveness in the areas of finance, information technology, and human resources. Tim graduated Rutgers University with a bachelor’s degree in Accounting and received his master’s degree in Business Management from Fairleigh Dickinson University.

He brings an extensive background in financial and operational management as well as strong leadership skills honed through many years of senior executive positions in the private and public sectors working with for-profit and not-for-profit organizations.

Tim’s professional career includes senior leadership positions with AT&T, Lucent Technologies, Avaya, Arc eConsultancy, AdvantEdge Healthcare, and Grand Street Settlement, where he held

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positions such as Chief Operating Officer, Chief Financial Officer, Senior Vice President, Controller, and Board Reporting Director.

Tim has also served as a member of the Board of Directors for Arc eConsultancy, Inc. After a 30-year career with for-profit corporations, Tim decided to pursue his interest in the not-for-profit realm. He helped Grand Street Settlement, a social services non-profit organization that provides educational, health, and wellness assistance to families and individuals in need on the lower east side of Manhattan and the Williamsburg section of Brooklyn, New York to improve their financial and operational performance as they worked toward their 100th anniversary of service to their community. He was recognized for his strong technical and leadership skills as well as his ability to communicate financial and operational results to non-financial staff, the Board of Directors, and other constituents of the Grand Street Settlement.

Executive Director Roque Calvo commented that, “Tim joined ECS at a time when we needed greater operational support to manage the changing landscape of the scholarly publishing industry. His financial, IT, and leadership experience have already paid dividends for ECS by building a strong operations foundation to advance our ability to disseminate technical content.”

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Institutional Member Spotlight: ZSW

by Dan Fatton

O

n Thursday, October 23, I accompanied ECS President Paul Kohl on a visit to ZSW, the Center for Solar Energy and Hydrogen Research in Ulm, Germany. Werner Tillmetz, Director of the Electrochemical Energy Technologies Division, and Mario Wachtler, Head of the Electrochemistry Team, graciously hosted our visit and provided an overview of the amazing work being done at their research facilities including the new eLaB. The ZSW site in Ulm has been focused specifically on batteries and fuel cells. Nearly 300 researchers (including the University of Ulm and the Helmholtz Institute Ulm for fundamentals) are working in electrochemistry, with a focus on advanced materials, electrode design, and pilot manufacturing for lithium ion batteries.

Much of the work at ZSW is conducted in partnership with industry.

For example, ZSW handles functional, lifetime, and safety testing for the automotive industry.

ZSW also has a department dedicated to materials research, which has 20+ years of experience in materials for lithium ion batteries, as well as options beyond lithium. A young researchers group has been working on a hybrid supercapacitor.

On the fuel cell side, there is a focus on characterization of fuel cell components, and fundamentals, including work on new membranes and catalysts, as well as stack design for automotive and other applications. The fuel cell test center at ZSW has 20 fully automated benches. ZSW has built more than 800 fuel cell stacks, and has achieved a continuous operation high lifetime of 20,000 hours.

Another ZSW facility in Stuttgart works on photovoltaics and energy policy, and ZSW also has solar test fields, both in Germany and Spain.

During our visit, the finishing touches were being made on the new eLaB facility in Ulm. It was certainly an impressive space, and the commitment to partnering with industry for practical application of research was noteworthy.

“It was a great pleasure to visit ZSW and tour the new building and battery facilities in Ulm. It is exciting to see these state-of-theart facilities come to life in Germany,” said Paul Kohl.

Dr. Tillmetz added, “The activities of ECS as the world leading network of electrochemists are of tremendous importance in a world where electrochemical energy technologies are now in the focus of many industry sectors.”

Werner Tillmetz (left), ZSW Head of the Electrochemical Energy Technologies Division, and Mario Wachtler (right), ZSW Head of Team Electrochemistry, with ECS President Paul Kohl (center) at the ZSW facility in Ulm.

It was a great pleasure to visit ZSW in Germany, and I’m looking forward to hearing about many more projects from the new site in the near future.

Dan Fatton is the Director of Development and Membership Services for ECS. He may be reached at dan.fatton@electrochem.org.

ECS Sponsored Meetings for 2015 In addition to the regular ECS biannual meetings and ECS Satellite Conferences, ECS, its Divisions, and Sections sponsor meetings and symposia of interest to the technical audience ECS serves. The following is a list of sponsored meetings for 2015. Please visit the ECS website for a list of all sponsored meetings.

•

2015 China Semiconductor Technology International Conference, March 17-19, 2015 — Shanghai, China

• 16th Topical Meeting of the International Society of Electrochemistry, March 22-26, 2015 — Angra do Reis, Brazil • 17th Topical Meeting of the International Society of Electrochemistry, May 31-June 3, 2015 — Saint-Malo, France • 66th Annual Meeting of the International Society of Electrochemistry, October 4-9, 2015 — Taipei, Taiwan To learn more about what ECS sponsorship could do for your meeting, including information on publishing proceeding volumes for sponsored meetings, or to request an ECS sponsorship of your technical event, please contact ecs@electrochem.org.

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DIVISION NEWS Battery Division

The Battery Division held its Division luncheon in Cancun on Tuesday, October 6, 2014. Martin Ebner (pictured on the left) received the Battery Division Student Research Award. Ram Manthiram (right) received the Battery Division Research Award. Pictured in the center is Bor Yann Liaw, Chair of the Battery Division.

(Photograph by Shirley Meng, Battery Division Treasurer.)

Electrodeposition Division

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he Electrodeposition Division Research Award was established in 1979 to recognize outstanding research contributions for the field of electrodeposition. The 2014 award recipient was Alan West from Columbia University and he received the award for his contributions in modeling of the electrochemical systems. Dr. West was acknowledged at the Division luncheon on Wednesday, October 13, 2014, at the fall ECS meeting in Cancun. Giovanni Zangari, chair of the Division, presented him with the award plaque and check for $2000. The same day, Dr. West presented his award lecture, “Mathematical Modeling in Electrodeposition Studies.”

The Electrodeposition Division Research Award winner Allan West (left) is receiving his award from Division Chair Giovanni Zangari.

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Dielectric Science and Technology Division and Electronic and Photonic Division: A Symposium Award

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he Symposium on Semiconductors, Dielectrics, and Metals for Nanoelectronics 12, sponsored by the Dielectric Science and Technology Division and the Electronic and Photonic Division, gave the Best Paper Award at the 2014 joint ECS and SMEQ meeting in Cancun, Mexico for the papers presented at the 2013 symposium held in San Francisco, California during the 224th ECS meeting. The best paper award winners were Michel Houssa, Valery Afanasiev, Katsumasa Kamiya, and Daniele Ielmini for their respective papers: • “Interaction of Germanene with (0001)ZnSe Surfaces: A Theoretical Study,” by M. Houssa, E. Scalise, B. van den Broek, G. Pourtois, V. V. Afanas’ev, and A. Stesmans • “Electron Band Alignment At Ge/Oxide and AIII-BV/Oxide Interfaces From Internal Photoemission Experiments,” by V. V. Afanas’ev, H. Y. Chou, M. Houssa, and A. Stesmans • “Theoretical Design of Desirable Stack Structure for Resistive Random Access Memories,” by K. Kamiya, M. Y. Yang, B. Magyari-Kope, M. Niwa, Y. Nishi, and K. Shiraishi • “Resistive Switching in Metal Oxides: From Physical Modeling to Device Scaling,” by D. Ielmini, S. Balatti, and S. Ambrogio This symposium introduced the Best Paper Award at its third run (Los Angeles, 2005) in the series on high dielectric constant gate stacks. The first of these best paper awards was won by Maureen MacKenzie of the University of Glasgow, UK, on the basis of her presentation and her manuscript entitled, “Advanced Nano-Analysis of High-Κ Dielectric Stacks.” The award was made possible by a donation from Anelva Corporation (now part of Canon Inc.) of Japan, and consisted of a citation and a check for $1000.

The second Best Paper Award, given in the 2006 Cancun symposium (again facilitated by a donation from the Canon Anelva Corporation, Japan), was won by Daniel Lichtenwalner of North Carolina State University, on the basis of the quality of both the manuscript and the presentation, entitled “Reliability and Stability Issues for Lanthanum Silicate as a High-K Dielectric.”

For the Washington, D.C. symposium in 2007, two Best Paper Awards were given, one for the best presentation, and another for the best ECS Transactions manuscript. Both awards consisted of a citation and a check for $1000, and were made possible by donations from the Canon Anelva Corporation, Japan, Semiconductor Diagnostics Incorporated, Tampa, Florida, and Aixtron AG, Aachen,

Germany. While the best manuscript award was won by Koji Kita of the University of Tokyo, on the basis of the quality of the manuscript entitled “Dramatic Improvement of GeO2/Ge MIS Characteristics by Suppression of GeO Volatilization,” the best presentation award was won by Carlos Driemeier of the Universidade Federal do Rio Grande do Sul, Porto Alegre, Brazil on the basis of his presentation entitled “Oxygen Species in HfO2 Films: An in situ X-Ray Photoelectron Spectroscopy Study.”

In 2008 at the Honolulu, Hawaii symposium, the best manuscript award was won by Kouichi Muraoka of the Toshiba Corporation, Japan on the basis of the quality of the manuscript entitled “Interface Engineering of a Metal/High-k/Ge Layered Structure by Water Vapor Discharge,” and the best presentation award was won by Robert Wallace of the University of Texas, USA on the basis of his presentation entitled “In-Situ Studies of Interfacial Bonding of High-k Dielectrics for CMOS Beyond 22 nm.”

At the Vienna, Austria symposium (2009), the award winners were Paul Hurley for the best presentation and Geoffrey Pourtois for the best manuscript for their papers: “Structural and Electrical Properties of HfO2/InxGa1-xAs Structures (x = 0, 0.15, 0.3, and 0.53),”

by Paul Hurley; and “Modeling of Alternative High-k Dielectrics for Memory Based Applications,” by G. Pourtois, S. Clima, K. Sankaran, P. Delugas, V. Fiorentini, W. Magnus, B. Soree, S. Van Elshocht, C. Adelman, J. Van Houdt, D. Wouters, S. DeGendt, M. M. Heyns, and J. Kittl.

In 2010 at the Las Vegas, Nevada symposium, the award winners were Eduard Cartier for the best presentation and Masaharu Oshima for the best manuscript. Their respective papers were: “The Role of Oxygen in the Development of Hf-Based High-k/Metal Gate Stacks for CMOS Technologies,” by E. A. Cartier, and “Synchrotron Radiation Photoelectron Spectroscopy of Metal Gate/HfSiO(N)/ SiO(N)/Si Stack Structures,” by M. Oshima, S. Toyoda, H. Kamada, T. Tanimura, Y. Nakamura, K. Horiba, and H. Kumigashira.

At the Boston, Massachusetts symposium in 2011, we reverted to the best paper for both the manuscript and the presentation and the award winner was Shinichi Takagi for his paper “MOS Interface Control Technologies for III-V/Ge Channel MOSFETs,” by S. Takagi, R. Zhang, T. Hoshii, and M. Takenaka.

At the Honolulu, Hawaii symposium (2012), the best paper award winner was Takahide Umeda for his paper “SiC MOS Interface States: Similarity and Dissimilarity from Silicon,” by T. Umeda, R. Kosugi, Y. Sakuma, Y. Satoh, M. Okamoto, S. Harada, and T. Ohshima.

This item was contributed by Durga Misra (New Jersey Institute of Technology).

Samares Kar, lead organizer of the symposium on Semiconductors, Dielectrics, and Metals for Nanoelectronics 12, (at left in all three photos), presents the Best Paper Award to Michel Houssa (left photo), Valery Afanasiev (center photo), and Kenji Shiriashi (right photo), who is accepting the award for Katsumasa Kamiya. The fourth award winner, Daniel Ielmini, was unable to attend the meeting.

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New Division Officers New officers for the 2014-2016 terms have been elected for the following Divisions.

Battery Division Chair Robert Kostecki, Lawrence Berkeley National Laboratory Vice-Chair Christopher Johnson, Argonne National Laboratory Secretary Marca Doeff, Lawrence Berkeley National Laboratory Treasurer (Ying) Shirley Meng, University of California at San Diego Members-at-Large Khalil Amine, Argonne National Laboratory Yi Cui, Stanford University Kristina Edstrom, Uppsala University Dominique Guyomard, CNRS - Univ de Nantes Richard Jow, U. S. Army Research Laboratory Brett Lucht, University of Rhode Island John Muldoon, Toyota Research Institute of North America Martin Winter, Westfalische Wilhelms-Universitat Marina Yakovleva, FMC Corp

Corrosion Division Chair Rudolph Buchheit, Ohio State University Vice-Chair Sannakaisa Virtanen , University of ErlangenNuremberg Secretary/Treasurer Masayuki Itagaki, Tokyo University of Science Members-at-Large Nick Birbilis, Monash University Devicharan Chidambaram, University of Nevada, Reno Philippe Marcus, CNRS-ENSCP (UMR 7045) H. Neil McMurray, University of Wales, Swansea Nancy Missert, Sandia National Laboratories James Noel, University of Western Ontario

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Sensor Division Chair Bryan Chin, Auburn University Vice-Chair Nianqiang Wu, West Virginia University Secretary Ajit Khosla, Lab177 Inc. Treasurer Jessica Koehne, NASA Ames Research Center Members-at-Large Zoraida Aguilar, Zystein, LLC Sheikh Akbar, Ohio State University Cynthia Bruckner-Lea, Pacific Northwest National Laboratory Ying-Lan Chang, Nanomix Jay Grate, Pacific Northwest National Laboratory Peter Hesketh, Georgia Tech A. Robert Hillman, University of Leicester Gary Hunter, NASA Glenn Research Center Tatsumi Ishihara, Kyushu University Sangmin Jeon, POSTECH Mira Josowicz, Georgia Tech Girish Kale, University of Leeds Christine Kranz, University of Ulm Pawel Kulesza, University of Warsaw Jing Li, NASA Ames Research Center Chung-Chiun Liu, Case Western Reserve University Vadim Lvovich, NASA Glenn Research Center Sushanta Mitra, York University Norio Miura, Kyushu University Rangachary Mukundan, Los Alamos National Laboratory Larry Nagahara, National Cancer Institute Antonio Ricco, Stanford University Michael Sailor, University of California at San Diego Christopher Salthouse, University of Massachusetts Praveen Kumar Sekhar, Washington State University Yasuhiro Shimizu, Nagasaki University Aleksandr Simonian, Auburn University Joseph Stetter, KWJ Engineering Inc. Thomas Thundat, University of Alberta Raluca Van Staden, NIRECM Petr Vanýsek, Northern Illinois University Liju Yang, North Carolina Central University

The Electrochemical Society Interface • Winter 2014

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ECS Division Contacts High Temperature Materials

Battery Robert Kostecki, Chair Lawrence Berkeley National Laboratory r_kostecki@lbl.gov • 1.510.486.6002 (U.S.) Christopher Johnson, Vice-Chair (Ying) Shirley Meng, Treasurer Marca Doeff, Secretary Corrosion Rudolph Buchheit, Chair Ohio State University buchheit.8@osu.edu • 1.614.292.6085 (U.S.) Sannakaisa Virtanen, Vice-Chair Masayuki Itagaki, Secretary/Treasurer Dielectric Science and Technology Dolf Landheer, Chair National Research Council - Canada dolf.landheer@nrc-cnrc.gc.ca • 1.613.993.0560 (Canada) Yaw Obeng, Vice-Chair Puroshothaman Srinivasan, Treasurer Vimal Desai Chaitanya, Secretary Electrodeposition Giovanni Zangari, Chair University of Virginia gz3e@virginia.edu • 1.434.243.5474 (U.S.) Elizabeth Podlaha-Murphy, Vice-Chair Philippe Vereecken, Treasurer Stanko Brankovic, Secretary Electronics and Photonics Andrew Hoff, Chair University of South Florida hoff@usf.edu • 1.813.974.4958 (U.S.) Mark Overberg, Vice-Chair Junichi Murota, Secretary Edward Stokes, 2nd Vice-Chair Fan Ren, Treasurer Energy Technology Adam Weber, Chair Lawrence Berkeley National Laboratory azweber@lbl.gov • 1.510.486.6308 (U.S.) Scott Calabrese Barton, Vice-Chair Vaidyanathan (Ravi) Subramanian, Treasurer Andrew Herring, Secretary

Xiao-Dong Zhou, Chair University of South Carolina zhox@cec.sc.edu • 1.803.777.7540 (U.S.) Turgut Gur, Sr. Vice-Chair Gregory Jackson, Jr. Vice-Chair Paul Gannon, Secretary/Treasurer

Industrial Electrochemistry and Electrochemical Engineering

Venkat Subramanian, Chair Washington University in St. Louis vsubramanian@seas.wustl.edu • 1.314.935.5676 (U.S.) Douglass Reimer, Vice-Chair John Staser, Secretary/Treasurer

Luminescence and Display Materials Anant A. Setlur, Chair GE Global Research Center setlur@ge.com • 1.518.387.6305 (U.S.) Madis Raukas, Vice-Chair Mikhail Brik, Secretary/Treasurer

Nanocarbons R. Bruce Weisman, Chair Rice University weisman@rice.edu • 1.713.348.3709 (U.S.) Slava V. Rotkin, Vice-Chair Dirk Guldi, Treasurer Hiroshi Imahori, Secretary

Organic and Biological Electrochemistry James Burgess, Chair Case Western Reserve University jdb22@po.cwru.edu • 1.216.368.4490 (U.S.) Mekki Bayachou, Vice-Chair Graham Cheek, Secretary/Treasurer Physical and Analytical Electrochemistry Robert Mantz, Chair Army Research Office robert.a.mantz@us.army.mil • 1.919.549.4309 (U.S.) Pawel Kulesza, Vice-Chair Alanah Fitch, Treasurer Andrew Hillier, Secretary Sensor Bryan Chin Auburn University bchin@eng.auburn.edu • 1.334.844.3322 (U.S.) Nianquiang Wu, Vice-Chair Ajit Khosla, Secretary Jessica Koehne, Treasurer

The Electrochemical Society Interface • Winter 2014

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websites of note

by Zoltan Nagy

Corrosion Electrochemistry and Kinetics

Two very detailed introductory websites of corrosion and its connection and measurements by electrochemistry.

• P. R. Roberge, McGraw-Hill Professional • http://www.mhprofessional.com/downloads/products/0071482431/RobergeCh3.pdf • http://www.mhprofessional.com/downloads/products/0071482431/RobergeCh5.pdf

Cathodic Protection

A series of a large number of papers dealing with all aspects of cathodic protection, theory, and applications.

• Deepwater Corrosion Services • http://www.stoprust.com/technical-library.htm

Kinetics of Aqueous Corrosion

A very good series of teaching material about corrosion and its connection to electrochemistry, with practical applications.

• Dept of Materials Science and Metallurgy, (U. of Cambridge) • http://www.doitpoms.ac.uk/tlplib/aqueous_corrosion/index.php

Anodic Protection: Its Operation and Applications

Detailed theory and applications of anodic protection, which somehow nowadays does not seem very practical, though it made big news about fifty years ago.

• J. I. Munro and W. W. Shim, Corrosion Service Co. Ltd • http://www.westcoastcorrosion.com/Papers/13104%20AP%20Operation%20&%20Apps.pdf

About the Author

Zoltan Nagy is a semi-retired electrochemist. After 15 years in a variety of electrochemical industrial research, he spent 30 years at Argonne National Laboratory carrying out research on electrode kinetics and surface electrochemistry.

Presently he is at the Chemistry Department of the University of North Carolina at Chapel Hill. He welcomes suggestions for entries; send them to nagyz@email.unc.edu.

In the •

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The spring 2015 issue of Interface will be a special issue on photovoltaics and electric vehicles, entitled, “PV, EV, and Your Home,” that will be guest edited by James M. Fenton, Director of the Florida Solar Energy Center (FSEC), University of Central Florida. The issue will feature the following articles (tentative list): “PV, EV, and Your Home,” by James M. Fenton; “PV and Battery Storage for Your Home and Business,” by Dave Click, FSEC; “V2G,” by Rich Raustaud, FSEC; “Fuel Cells, H2 Generation at Home – Backup Power Options,” by Paul Brooker, FSEC; and “Fast and Wireless Charging,” by Charles Botsford and Andrea Edwards, AeroVironment and Qualcomm.

issue of •

ECS Spring 2015 Meeting in Chicago ... The spring issue will feature a special section on the upcoming ECS meeting, with information on special lectures and symposia.

•

Tech Highlights continues to provide readers with synopses of some of the most interesting papers published in the ECS journals. As an added bonus, the full text of all of the articles mentioned in this column are freely accessible in the ECS Digital Library.

•

Don’t miss the next edition of Websites of Note, which gives readers a look at some little-known, but very useful sites.

The Electrochemical Society Interface • Winter 2014

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To be eligible for the promotion, the instrument and sampling accessories, autosamplers, software, service plans or consumables must be included on the same Electrochemical Society Interface • Winter 2014 purchase order. Not valid for process analyzers or with any other offer or promotion. Some exclusions may apply, contact marketing for a complete list of exclusions.

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Why Go Open Access at ECS SOCIE T Y NE WS

Reach more readers

OA for FREE!

ECS offers Author Choice Open Access, giving you the opportunity to make your papers Open Access (OA) – available to any scientist (or anyone, for that matter) with an Internet connection, and increasing your pool of potential readers.

You can publish your papers as Open Access for FREE if you have an Article Credit. Authors who are ECS members, who have attended a recent ECS meeting, or who are coming from subscribing institutions qualify. Those who cannot claim an Article Credit will be asked to pay an $800 Article Processing Charge to make their papers Open Access – a fee ECS continues to keep low.

Quality publications The research published in our journals (Journal of The Electrochemical Society, ECS Journal of Solid State Science and Technology, ECS Electrochemistry Letters, and ECS Solid State Letters) is truly at the cutting edge of our technical arenas, and ECS publications have continued to focus on achieving quality through a high standard of peer-review. Our four peer-reviewed titles are among the most highly-regarded in their areas.

Choosing to make your paper Open Access within these journals makes no difference to the quality processes we uphold at ECS— selection criteria and peer review remain exactly the same. The difference is in who can see your content. Papers not published as Open Access can only be read by either those from a subscribing institution, or those who are willing to pay a fee to access it. Make your work more accessible by making it OA.

Keep your copyright ECS’s Open Access publishing agreement with authors does not require a transfer of copyright: the copyright remains with the author.

Authors, however, must choose what kind of license they want to grant their readers, and ECS offers a choice of two Creative Commons usage licenses that authors may attach to their work (see sidebar).

Save the World Next time you submit a paper; why not make it Open Access?

Electrochemistry and solid state science research is helping scientists and researchers across the globe solve problems facing our modern world, and the more people who can access your work, the faster those problems may be solved. If you have any questions about our Open Access program, please visit www. electrochem.org/oa or email us at oa@electrochem.org.

A WORD ABOUT COPYRIGHT 4

When publishing OA the copyright remains with the author.

4

The author selects one of two Creative Commons (CC) usage licenses defining how the article may be used by the general public.

4

CC BY license is the most liberal allowing for unrestricted reuse of content, subject only to the requirement that the source work is appropriately attributed.

4

CC BY-NC-ND license is more similar to the current usage rights under the transfer of copyright agreement: it limits use to noncommercial use (NC), and restricts others from creating derivative works(ND).

Find out more at

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electrochem.org/oa

The Electrochemical Society Interface • Winter 2014

Beyond Open Access

by Mary Yess “The future is already here, it’s just not very evenly distributed.”

—William Gibson

T

he models of scientific communication and publication— which have served us all so well for so long—are no longer fully meeting the spirit of the ECS mission, may not be financially viable, and are hurting the dissemination of the results of scientific research.

The future of Open Access (OA)1 can change not only scholarly publishing, but can change the nature of scientific communication itself. OA has the power to more “evenly distribute” the advantages currently given to those who can easily access the outputs of scientific research.

ECS has long been concerned with facilitating that access, and our mission2 has been to disseminate the content from within our technical domain, as broadly as possible, and with as few barriers as possible. To accomplish this, we have maintained a robust, highquality, high-impact publishing program for over 100 years.

Several years ago, ECS started taking a serious look at the challenges facing us in fulfilling our mission, specifically with respect to our publishing program. The challenges—faced by others in publishing, to a greater or lesser degree—are many and have become increasingly severe:

• the lure of profits to be made, resulting in more competing journals being launched with greater frequency, both by reputable publishers and start-ups only in it for the money (the latter often referred to as “predatory” publishers).4 When a commercial scientific publisher is taking a 35% net profit out of the system,5 compared with under 2% by ECS, something is not only wrong, but it is clear that some publishers will do anything and everything they can to keep maintaining that level of profit. For many, journal publishing has indeed become a business.

Adding to Researcher Responsibilities While open access is still a very low priority for many authors,6 especially within the technical areas covered by ECS, mandated OA publishing requirements are quickly taking hold and being implemented.

The “Finch Report” in 2012 set UK on its way to mandated OA.7 In the U.S., OA finally gained some traction in March 2013 when the U.S. Office on Science & Technology Policy (OSTP) announced (continued on next page)

• a longtime erosion of subscriptions revenue and of subscribers; • competition from (primarily) commercial publishers that game the impact factor system, and impose “big deal” packages of subscriptions on libraries; • reduced library budgets that at first severely affected book budgets and now seriously affect serials budgets; • increasing costs of online publishing;3 • consolidation in the publishing industry, leading to the extinction of small publishers; and

The Electrochemical Society Interface • Winter 2014

“

OA has the power to more “evenly distribute” the advantages currently given to those who can easily access the outputs of scientific research.

”

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(continued from previous page)

that U.S. government agencies with budgets of $100m+ must develop plans to make available to the public publications reporting federally funded research.8 The Department of Energy became the first agency to announce a policy in this regard.9 Many academic institutions have established policies in support of disseminating the fruits of their research and scholarship as widely as possible, through different mechanisms, but most often by requiring faculty to deposit their work in the institution’s repository. For example, the Massachusetts Institute of Technology (MIT) has a policy10 where each faculty member grants to MIT nonexclusive permission to make available his or her scholarly articles and to exercise the copyright in those articles for the purpose of open dissemination. The faculty member makes available an electronic copy of the final version of the manuscript to a designated representative at MIT. That office then makes the scholarly article available to the public in an open-access repository. (To learn if your institution has a mandatory archiving policy, visit the ROARMAP site.11)

“

“Free the ScienceTM”: to provide all ECS content at no cost to anyone—no fees for authors, readers, and libraries.

”

The landscape of OA mandates is becoming increasingly complex: with much research now being done across multiple institutions and multiple countries, authors will be subject to multiple mandates— from funding agencies and from their home institutions—creating an increased administrative burden for researchers. CHORUS (Clearinghouse for the Open Research of the United States)12 and SHARE13 are two efforts currently underway to make compliance easier.

CHORUS is a suite of services that provides a solution for agencies and publishers to deliver public access to published articles reporting on funded research in the United States. This nonprofit leverages widely-used technology to facilitate the compliance process. (Scaling for international needs is being discussed, but is not a main focus of the organization.)

The Shared Access Research Ecosystem (SHARE) is a higher education and research community initiative to ensure the preservation of, access to, and reuse of research outputs. SHARE will develop solutions take advantage of the interest shared by researchers, libraries, universities, funding agencies, and other key stakeholders to disseminate research.

ECS’s Open Access Goals For many societies, the ever-increasing publishing challenges (noted above) have been too daunting, and many have decided to enter into publishing arrangements with commercial publishers, or to sell their journals outright. In doing so, some societies have been able to retain their control over the editorial process (including peer review14), the quality of their journals, and their brand identity; but some have not.

After evaluating the Society’s current situation vis-à-vis publications, and after many discussions among volunteer leadership about the challenges facing ECS as a publisher, the Board of Directors reaffirmed the Society’s commitment to continue its high-quality publications program. We viewed the situation from a financial viability standpoint and from the standpoint of “what’s the right thing to do?” To maintain our commitment, ECS would need to take a unique position. That position was centralized around an 32

Open Access program; and in May 2013, the Society established its Open Access goals, in two phases: an immediate hybrid plan and a longer-term plan.15 In February 2014, the Society launched the first phase: Author Choice Open Access. Authors choose to: (a) make their articles OA [pay Article Processing Charges (APCs) or take advantage of the Society’s many article credit offerings16]; or (b) have their articles remain part of the subscriptions-based set of articles. This phase meets the need of authors by providing an Open Access publication option for those that must meet funder or institutional mandates, while the Society develops its longer-term plan.

As of this writing (November 20), 273 OA papers have been published, primarily in the flagship Journal of The Electrochemical Society. The top three countries from which authors are requesting OA are the U.S., Japan, and China; and about half the requesters are ECS members.

To support the high costs of publishing the journals, and until the next phase of the program can be put into place, ECS will use both author payments and library payments, hence the term “hybrid” Open Access. The plan augments our commitment to our constituency: for authors, to not charge high APCs; and for libraries, to not “doubledip.” In addition, for our library supporters, for the third year in a row, ECS will not raise subscription prices.

The unique, and longer-term part of our OA plan is to “Free the ScienceTM”: to provide all ECS content at no cost to anyone— no fees for authors, readers, and libraries. Our pledge to the community is that we will continue to decrease subscription fees and APCs every year until we get as close to completely free as we can.

To that end, the Society will be undertaking a ten-year fund-raising campaign to grow the Society’s Publications Endowment.

If nothing else, through our Open Access pledge, ECS can help bring some sanity back to the very broken subscription-based publishing model.

More Needs to Be Done Where does open access go from here? Even though OA has taken hold, and become a “standard” in publishing, the OA landscape has become more bewildering, with many types of OA, many types of author mandates, and many types of licensing.15 ECS thinks of itself not as a publisher per se, but as a “conduit”—getting the content to and from researchers—and our job now, in our role as a scholarly society, is to continue working on the best ways to support authors and readers in compliance and access.

“

Others have moved on from “open access” to “open science”—the concept of opening up all aspects of scientific research to allow others to follow the process and collaborate.

”

Through its meetings and publications, ECS has long been a highlyrespected venue for researchers to come together to discuss their work in a highly-engaged community of like-minded people from around the world and from many settings (academic, government, corporate).

Looking past Open Access “1.0,” there are many more challenges and opportunities; and with ECS well established in its OA plans, it’s time to think about how else we can best support the science.

As Interface Co-Editor Vijay Ramani pointed out in his fall 2014 editorial, “Free the Engineering,”17 in which he refers to the unfortunate trends in the manufacturing sector that have held back the field, the same mistakes are repeated by different manufacturers who The Electrochemical Society Interface • Winter 2014

remain unaware of past failures that invariably remain unpublished.

He suggested that ECS might “play a role in alleviating this issue by providing a platform for a summit or forum wherein details relevant to selected past (failed or defunct) approaches/processes are collated and presented…”—an intriguing idea.

“

Be an advocate. Who wouldn’t want to contribute to faster problem solving, encourage innovation, enrich education, and stimulate the economy?

”

Others in the field, such as The Open Science Project,18 have proposed bolder steps to encourage transparency in experimental methodology, observation, and collection of data.

Still others have moved on from “open access” to “open science”— the concept of opening up all aspects of scientific research to allow others to follow the process and collaborate. The concept often includes open access, but also experiments with open peer review and post-publication peer review. Other tantalizing ideas in “open science” include: open notebook science, citizen science, aspects of open source software, and crowd-funded research projects.19

How You Can Help Free the ScienceTM Developing our Open Access plan was not simply a matter of deciding what APCs to charge. It was a matter of setting a course as stewards of our science. And our science has become more important than ever because electrochemistry has become vital to solving worldwide challenges in energy, water, and sanitation.

We need your help.

Help break the reliance on “the” impact factor. It’s a metric for a whole journal, and not a useful metric when considering an individual for graduation, for tenure, or for a promotion or salary increase.

Whenever you can, make a conscious decision to publish at least one of your papers each year in an OA journal—one with author and reader interests at heart.

Support the ECS Publications Endowment.20 We envision publication costs not being borne by subscribers, nor by authors, but

by ECS. This will require fund-raising, leveraging support of other programs to free up operational revenues, careful management of the Society’s expenses, cutting costs, and building our established endowment.

Be an advocate. Who wouldn’t want to contribute to faster problem solving, encourage innovation, enrich education, and stimulate the economy?

Mary Yess is the Society’s Deputy Executive Director and Publisher mary.yess@electrochem.org ORCID #: http://orcid.org/0000-0003-3909-6524

References 1. For a comprehensive introduction to Open Access (OA), Peter Suber’s article continues to be a good starting point: http://legacy. earlham.edu/~peters/fos/overview.htm.

2. The ECS mission is “to advance theory and practice at the forefront of electrochemical and solid state science and technology, and allied subjects. To encourage research, discussion, critical assessment, and dissemination of knowledge in these fields, the Society holds meetings, publishes scientific papers, fosters training and education of scientists and engineers, and cooperates with other organizations to promote science and technology in the public interest.”

The Electrochemical Society Interface • Winter 2014

3. While there are many who feel that online publishing doesn’t cost much (because there are no print and postage costs, among other reasons) the opposite is true. There are many components to preparing an article with many inter-operability features, to be hosted in perpetuity, etc. These increase costs every year; that, however, is the subject for another article.

4.

J. Sanchez, “Predatory Publishers Are Corrupting Open Access,” Nature, 489, 179 (13 September 2012), doi:10.1038/489179a, http://www.nature.com/news/predatorypublishers-are-corrupting-open-access-1.11385; D. Butler, “Investigating Journals: The Dark Side of Publishing,” Nature, 495, 433 (28 March 2013), doi:10.1038/495433a, http://www. nature.com/news/investigating-journals-the-dark-side-ofpublishing-1.12666; Scholarly Open Access list of questionable publishers: http://scholarlyoa.com/publishers/.

5. Just a few of the many articles on the profits of commercial publishers: http://www.economist.com/node/21545974; http:// poeticeconomics.blogspot.com/2012/01/enormous-profits-ofstm-scholarly.html; http://svpow.com/2012/01/13/the-obsceneprofits-of-commercial-scholarly-publishers/.

6. NPG/Palgrave Release Author Insights Survey, published October 22, 2014: http://www.thebookseller.com/news/ npgpalgrave-release-author-insights-survey; Taylor & Francis Open Access Survey: Exploring Authors Views of Taylor & Francis and Routledge Authors: http://septentrio. uit.no/index.php/SCS/article/view/3134; Generation Gap in Authors’ Open Access Views and Experience, Reveals Wiley Survey: http://www.wiley.com/WileyCDA/PressRelease/ pressReleaseId-109650.html.

7. Open Access in UK: http://www.researchinfonet.org/publish/ finch/; http://www.hefce.ac.uk/whatwedo/rsrch/rinfrastruct/oa/ policy/ 8. U.S. Office on Science & Technology Policy memo: http://www. whitehouse.gov/blog/2013/02/22/expanding-public-accessresults-federally-funded-research 9. The U.S. Department of Energy’s public access plan: http:// energy.gov/downloads/doe-public-access-plan 10. http://libraries.mit.edu/scholarly/mit-open-access/open-accessat-mit/mit-open-access-policy/. MIT has been pro-active in getting the word out to its authors, and this writer participated in a panel discussion for MIT faculty and students: http://libraries. mit.edu/news/chemistry-open/16463/.

11. Registry of Open Access Repositories Mandatory Archiving Policies: http://roarmap.eprints.org/ 12. http://www.chorusaccess.org/ 13. http://www.arl.org/focus-areas/shared-access-researchecosystem-share 14. In ECS’s Open Access program, the Society continues to maintain its strict standards of peer review.

15. The main Web page about the Society’s Open Access program is http://www.electrochem.org/oa/. An earlier Interface story about the plan may be found at http://www.electrochem.org/dl/ interface/spr/spr14/spr14_p09_11.pdf.

16. If you’re an ECS member, you get an article credit. If you attend an ECS meeting, you get an article credit. One of the biggest waivers we put in place was for libraries. If your library subscribes to any of our titles, that institution has unlimited article credits for its faculty and students.

17. V. Ramani, “Free the Engineering,” Interface, 23(3), 3 (2014); http://www.electrochem.org/dl/interface/fal/fal14/fal14_p003. pdf 18. The Open Science Project: http://www.openscience.org/blog/?p=269.

19. What Is Open Science: http://blog.f1000research.com/2014/11/11/ what-is-open-science/.

20. http://www.electrochem.org/development/

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A Case for Open Access: Accelerating Discovery in Climate Science

by Dan Fatton “Comprehensive scientific assessments of our current and potential future climates clearly indicate that climate change is real, largely attributable to emissions from human activities, and potentially a very serious problem.” This is taken from a public policy statement originally written in 2004 by the American Chemical Society.1 Eighteen scientific societies signed on to a similar American Association for the Advancement of Science statement affirming the consensus scientific view on climate change in 2009.2 According to the California Governor’s Office of Planning and Research,3 at least 200 worldwide scientific organizations now formally hold the position that climate change has been caused by human action.

The International Panel on Climate Change (IPCC) was set up in 1988 to assess global warming and its impacts. Recently, the panel released a major report, capping its latest assessment, a mega-review of 30,000 climate change studies that establishes with 95% certainty that nearly all warming seen since the 1950s is due to human activity.

More than 700 of the world’s top climate scientists and 1,729 expert reviewers from more than 70 countries participated in the report preparation process.

The latest report reinforces with medium to high confidence levels some of the basic science concerning climate change: • Each of the last three decades has been successively warmer at the earth’s surface than any preceding decade since 1850. The period from 1983 to 2012 was very likely the warmest 30-year period of the last 800 years in the northern hemisphere (high confidence), and likely the warmest 30-year period of the last 1,400 years (medium confidence).

• Ocean warming dominates the increase in energy stored in the climate system, accounting for more than 90% of the energy accumulated between 1971 and 2010 (high confidence), while only about 1% of that energy is stored in the atmosphere.

• Glaciers have lost mass and contributed to sea-level rise throughout the 20th century. The rate of ice mass loss from the Greenland ice sheet has very likely substantially increased over the period 1992 to 2011, resulting in a larger mass loss over 2002 to 2011 than over 1992 to 2002.

• Over the period 1901 to 2010, the global mean sea level rose by 0.19 ± 0.02 m. The rate of sea-level rise since the mid-19th century has been larger than the mean rate during the previous two millennia (high confidence).

• Atmospheric concentrations of greenhouse gases (GHG) are at levels that are unprecedented in at least 800,000 years. Concentrations of CO2, CH4, and N2O have all shown large increases since 1750 (40%, 150%, and 20%, respectively).

• Total annual anthropogenic GHG emissions have continued to increase from 1970 to 2010 with larger absolute increases between 2000 and 2010 (high confidence).

To summarize the latest report, “It is extremely likely that more than half of the observed increase in global average surface temperature from 1951 to 2010 was caused by the anthropogenic increase in greenhouse gas concentrations and other anthropogenic forcings together.”4

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More troubling than the confirmation of this science, which many have long considered settled, are the projections for future impacts and the truly daunting emission reductions that are projected to be necessary to avoid disruptive, and potentially catastrophic, changes in the future.

As the latest IPCC report notes in the Extreme Events section, “Impacts from recent climate-related extremes, such as heat waves, droughts, floods, cyclones, and wildfires, reveal significant vulnerability and exposure of some ecosystems and many human systems to current climate variability (very high confidence).

Impacts of such climate-related extremes include alteration of ecosystems, disruption of food production and water supply, damage to infrastructure and settlements, human morbidity and mortality, and consequences for mental health and human well-being.”5

“We must do more to limit greenhouse gas emissions if we want any chance of keeping global temperature change below 2°C relative to pre-industrial levels.”

The disproportionate impacts of climate change are also underscored, “Climate-related hazards exacerbate other stressors, often with negative outcomes for livelihoods, especially for people living in poverty (high confidence). Climate-related hazards affect poor people’s lives directly through impacts on livelihoods, reductions in crop yields, or the destruction of homes, and indirectly through, for example, increased food prices and food insecurity.”6 This September, I joined more than 400,000 others for the Peoples Climate March in New York City. I was encouraged by the “We Have the Solutions” contingent of the march, which included several groups of scientists. Many of us have been demanding action on climate change from our leaders, including those that attend the Climate Summit negotiations. For me, the latest IPCC report simply reinforces what I’ve already understood: we must do more to limit greenhouse gas emissions if we want any chance of keeping global temperature change below 2°C relative to pre-industrial levels.

The report also reinforces that the conversion to a clean energy economy is already feasible, both economically and technologically.

Countries like Germany have been demonstrating the possibilities of renewable energy, despite having sunshine profiles similar to that of Alaska. Of course, the Energiewende transition has not been without growing pains, and most would agree we must address the underlying energy storage issues to fully realize the potential of renewable energy sources like sun, wind, and water. Thankfully, we know the scientists of ECS are working on exciting research to improve our understanding and technological capabilities in batteries, photovoltaics, nanotechnology, and fuel cells, among other cuttingedge fields.

In 2013, the ECS board of directors made a bold, strategic decision to pursue open access. The push for transformation is being driven by a desire to disseminate scientific research and make it more widely accessible, to spread theoretical and practical knowledge that will advance scientific understanding. In March, after launching author choice open access, ECS published its first open access paper in the Journal of The Electrochemistry. Since then, there has been a strong demand for open access publication, with more than 214 papers published as open access as of October. Yet, to be truly open access and to create the most freedom possible for research that may affect the sustainability of our planet, we want to remove all financial The Electrochemical Society Interface • Winter 2014

barriers in ECS publications. Making the scientific research and data in ECS journals accessible to anyone with an internet connection will only inspire more discoveries, as well as more research and more innovation.

In my view, the bold pledge to move toward open access at ECS has serious implications for action on climate change. If we can make the scientific research results and latest findings published in ECS publications more widely accessible, we may speed up the scientific discovery process. Perhaps a young scientist in the developing world will unlock the key to some perplexing energy storage dilemma once weâ&#x20AC;&#x2122;ve made the latest findings more freely available in an ECS journal. Many of us believe we can accelerate the pace of innovation, and help solve critical challenges by opening access to scientific research. The urgency of the climate change crisis underscores the importance of this approach. You can support these efforts directly by donating to the ECS Publications Endowment.

References 1. http://www.acs.org/content/dam/acsorg/policy/publicpolicies/ promote/globalclimatechange/climate-change-positionstatement.pdf.

2. http://www.aaas.org/sites/default/files/migrate/ uploads/1021climate_letter1.pdf.

3. http://opr.ca.gov/s_listoforganizations.php.

4. Page 12, http://www.ipcc.ch/pdf/assessment-report/ar5/syr/ SYR_AR5_LONGERREPORT.pdf.

5. Page 16, http://www.ipcc.ch/pdf/assessment-report/ar5/syr/ SYR_AR5_LONGERREPORT.pdf.

6. Page 17, http://www.ipcc.ch/pdf/assessment-report/ar5/syr/ SYR_AR5_LONGERREPORT.pdf.

Dan Fatton is the Director of Development and Membership Services for ECS. He may be reached at dan.fatton@electrochem.org.

The Electrochemical Society Interface â&#x20AC;˘ Winter 2014

35

SOCIE PEOPLE T Y NE WS

2014 Nobel Prize – Ties to ECS

T

he Nobel Prize in Physics 2014 was awarded jointly to Isamu Akasaki, Hiroshi Amano, and Shuji Nakamura “for the invention of efficient blue light-emitting diodes which has enabled bright and energy-saving white light sources.” The investigation of light emitting materials is firmly established in the technical area of ECS and we are thrilled that the invention of efficient LEDs is deemed significant enough to deserve the Nobel Prize. We are even more thrilled that some of the awardees also have an association with ECS. Shuji Nakamura of University of California, Santa Barbara, was the plenary speaker at the 218th ECS meeting in Las Vegas. There, on Monday, October 11, 2010, he gave a presentation entitled “Current and Future Status of Nitride-based Solid State Lighting.”

Isamu Akasaki (Meijo University and Nagoya University, Nagoya, Japan) is a current ECS member. Hiroshi Amano is from Nagoya University, Nagoya, Japan. All three awardees have authored articles in the Journal of The Electrochemical Society and presently these articles are available to download for free. Please see the ECS Redcat Blog at http://www.ecsblog.org/awards/shuji-nakamura-awardednobel-prize/ for links to the articles.

The official Nobel Prize history page describes the events leading to the award considerations as follows: “When Isamu Akasaki, Hiroshi Amano and Shuji Nakamura produced bright blue light beams from their semi-conductors in the early 1990s, they triggered a fundamental transformation of lighting technology. Red and green diodes had been around for a long time, but without blue light, white lamps could not be created. Despite considerable efforts, both in the

36

scientific community and in industry, the blue LED had remained a challenge for three decades.” Now, the white LEDs for household use are becoming, though still a bit expensive, common place items.

The Nobel Laureates take center stage in Stockholm on 10 December, when they receive the Nobel Medal, Nobel Diploma and a document confirming the Nobel Prize amount from King Carl XVI Gustaf of Sweden.

New & Notab!e Henry S. White (ECS member 1985), a distinguished professor of chemistry and former chair of the University of Utah’s Department of Chemistry, will serve as the new dean of the University of Utah College of Science starting July 1, 2015.

Rodney S. Ruoff (ECS member from 2007-2011), distinguished professor at the Ulsan National Institute of Science and Technology (UNIST), South Korea, will receive the David Turnbull Leadership Award of MRS.

The Electrochemical Society Interface • Winter 2014

SOCIE PEOPLE T Y NE WS

In Memoriam memoriam Genelle Phillips Branneky (1926-2014)

G

Genelle Phillips Branneky

Branneky, (née Phillips), non-technical registration hostess for The Electrochemical Society meetings and wife of former Executive Director of The Electrochemical Society, died peacefully on Saturday, October 18, 2014.

Genelle Branneky was born on July 10, 1926 in St. Charles, Missouri. Her parents were the late Ersie and Clemens Phillips. She was preceded in death by her brother, Harlan, who died in 1972 at the age of 50. She is survived by her husband, V. H. “Bud” Branneky; her two daughters, SuAnne

The Electrochemical Society Interface • Winter 2014

enelle

B. Aune of Greer, South Carolina and Jane K. Branneky of West Palm Beach, Florida, and fifteen first cousins.

Genelle graduated from Lindenwood University in 1948. She was a volunteer at St. Luke’s Hospital in Missouri for ten years and a member of their Auxiliary. She married V. H. “Bud” Branneky, former Executive Director of The Electrochemical Society, in 1948.

Genelle Branneky became a volunteer hostess for the non-technical attendees at the semiannual meetings of The Electrochemical Society during Bud Branneky’s period as Executive Director from 19751991. She was a great ambassador for ECS and a familiar face at all the ECS meetings during Mr. Branneky’s term of service. She conveyed strong spousal and guest support and welcomed The Electrochemical Society family members to the meetings. Genelle also was active in the Women’s Club of Pennington and served as its President for several years.

The funeral was held on Wednesday, October, 22, 2014 at St. John United Church of Christ in St. Charles. For those wishing to make a memorial donation, the family suggests St. John UCC or FVC Employee Appreciation Fund (Friendship Village Chesterfield) 15201 Olive Blvd, Chesterfield, MO 63017.

37

ECS Classics Sherlock Swann, Jr.: Electro-organic Chemist and Master Bibliographer 1900-1983

by Richard Alkire

E

lectro-organic chemistry had its champion in Sherlock Swann, Jr. His scholarship, especially his massive bibliographic efforts, served singlehandedly to keep alive the promise and spirit of electro-organic chemistry in the U.S. from the 1930s to the 50s.

He was a charter member of the Electroorganic Division of The Electrochemical Society, formed in 1940, and was the first person to hold the offices of Secretary, ViceChair, and Chair of that Division. Beginning with his first ECS meeting in 1928 and continuing throughout his life, he played an active role in the Society, including a term as President in 1958-59. He was the Electroorganic Divisional Editor of the Journal of The Electrochemical Society, 1939-59; the Lifetime Honorary Chair of the Chicago Section; and was made an Honorary Member of the Society in 1974.

Swann was born in 1900 in Baltimore, Maryland, where his family had deep roots and a tradition of service to society. His great-grandfather, Thomas Swann, served as governor of Maryland, as mayor of Baltimore, as President of the Baltimore & Ohio Railroad, and was a leading force in the creation of Druid Hill Park, Baltimore’s first large municipal park. His father served as Baltimore police commissioner and subsequently as Postmaster, and led the reconstruction of downtown Baltimore and its streets after the Great Fire of 1904.

As a youth, Swann’s interests included electricity (in the form of a wireless transmitting set) and chemistry (learned in a preparatory school). He had already decided to be a chemist by the time he enrolled at Princeton University. He was introduced there by Dr. Menzies to the technique of searching the literature. He also took courses in metallurgy as well as voice and string quartets, all of which were topics that continued to be significant interests throughout his life. In addition, a family friend had advised him to take as much language as he could, an interest that eventually enabled him to read the literature in over a dozen languages. These experiences 38

influenced the course of his scientific career, both in bibliographic efforts, and in research on the effect of the electrode material on electro-organic reactions.

He was graduated from Princeton in the Class of ’22. As a graduate student in chemistry at Johns Hopkins, he carried out the reduction of acetone in sulfuric acid at a lead cathode in a laboratory course under Prof. Arthur Grollman, using the directions in Practical Methods of Electrochemistry by F. M. Perkin.1 He examined the literature and found papers on electro-organic chemistry,

which inspired him to specialize in the topic.

He was graduated as an organic chemist of the old school in 1926. He travelled to the Elektrochemisches Institut in Dresden, where he carried out experiments on the reduction of nitro compounds as described in Erich Müller’s Electrochemisches Praktikum.2 In his diary, Swann described his going-away party: “Before I left, I had the great good fortune to attend a German laboratory party. Bottles of beer, very probably the great Dortmunder

A young Swann in his riding habit. His love of horses continued throughout his life, “especially the ones with little silk numbers.”

The Electrochemical Society Interface • Winter 2014

Swann’s going-away party at the Electrochemisches Institute in Dresden. Swann sits at the center front, in a white lab coat, with host Erich Müller directly behind him.

Union, suddenly appeared in the dumb waiter and soon the students were squirting ‘Klosterwasser,’ the German Benedictine, into each other’s mouths from wash bottles, a lovely occasion indeed.”

The photograph above documents the charming event. This experience also gave Swann the opportunity to explore the treasures of European art and architecture, to which he returned many times over during his life. During this period he sought to meet Prof. Dr. Fr. Fichter, whose work he admired deeply, but was unable to make arrangements. It was another thirty years before that meeting took place, in Basel.

In 1927 he became a member of the Engineering Experiment Station attached to Chemical Engineering at the University of Illinois, where he received support from D. B. Keyes, Roger Adams, and Carl “Speed” Marvel. The next year, he attended his first ECS Meeting, in Bridgeport, Connecticut.

By 1934 he had launched a serious effort to gather the literature and, in 1935, published the first of many bibliographic collections.3 In 1937 he published a paper on industrial possibilities4 that in many respects predicted the significant impact that would subsequently be realized by development electrode and separator materials, as well as by improved cell design and engineering methods.

But it was his bibliographic skills that elevated this shy, quiet “scholar’s scholar” to international prominence. His relentless pursuit of the literature was truly astonishing The Electrochemical Society Interface • Winter 2014

and unprecedented. In the early years, all 80 sections of Chemical Abstracts were scanned. Later on, he found that relevant material appeared in only 22 sections, all of which were then scanned from the first issue on. Swann’s searches covered more than a century of literature published prior to the appearance of Chemical Abstracts, in 1907.

These sources included partial bibliographic abstracting reports of British, French, and German origins. For each, the dates were determined at which coverage had begun for each of the journals abstracted by these services, and the original literature of each journal was then scanned backward from that date to their first issue. The earliest publication was found in 1801.5 He found that the title and abstract of an article would not always mention the use of electrochemical techniques, especially preparative procedures.

Therefore every article was scanned in ten of the major journals published in Britain, Czechoslovakia, France, Germany, Japan, and the U.S. from their first issue.

Early patents, which predated coverage in Chemical Abstracts, were obtained by visits to patent offices throughout the world. Every attempt was made to arrive at a complete list of electro-organic synthesis patents in the English language.

Swann truly loved his calling as a “literature man” and pursued this lonely work with meticulous, painstaking attention to detail. His fascination and unprecedented devotion to the field of electro-organic chemistry at a time when it was in repose

Sherlock Swann, Jr., joined the University of Illinois in 1927, retired in 1969, and continued to come to his office almost daily through the early 1980s.

played a critical role in keeping it alive in the U.S. from the 1930s to the 50s. His chapter in the Technique of Organic Chemistry, published in 1956, stood for many years as the sole review in the English language.6 His deep conviction was that we can learn from the past. Indeed, over half of the electroorganic processes that, much later, were developed to the pilot plant or commercial scale, were known in the lab at the turn of the century. (continued on next page) 39

(continued from previous page)

In 1965 he concluded his search of the past literature, and from then on kept up with new literature as it appeared. In 1969 he retired and, at a dinner party he hosted for his colleagues, opened a bottle of sherry that had been in his family for over a century. He continued to come to his office almost every day for the remainder of his life.

Swann had a deep appreciation for classical as well as ethnic music and, over many years, acquired an enormous collection of recordings.

Many of these came from the Gramophone Shop, which was around the corner from the old ECS headquarters in New York City. One time the two of us attended an ECS Chicago Section meeting and found ourselves driving back to Urbana together, a 3-hour trip. After a brief conversation on politics and the stock market, topics that generally put him in a dour mood, he began to reminisce about his early interests in music. By the time we crossed the Illinois River at Kankakee, he was singing in high, light tenor voice. And for the next two hours he sang songs one after another that his father’s butler had taught him seventy years earlier.

In his Presidential Address to the Society in 1959, he recalled: “The first meeting that I attended was held in Bridgeport, Connecticut, in 1928. I went with Dr. W. C. Moore, who had previously persuaded me to become a member. I knew immediately that I was interested in the Society. That interest was not due to the papers that I listened to. There was nothing strictly on electro-organic on the program. I believe that it was due to the enthusiasm of the group, and the fact that I was made to feel that I belonged.”

What better advice could we have today for how best to promote the health of the Society?

In 1976, during the Annual Society Luncheon in Washington, DC, Stan Wawzonek put forward the suggestion that something really ought to be done to help Sherlock publish his bibliography.

We agreed to write a few letters to our industrial friends, to raise $5,000, and hire a secretary to type it up. But Sherlock had a very big surprise …. his collection was truly massive, well beyond anything that we had imagined. In due time, funds were contributed by 18 corporations, and the financial risk of publishing was underwritten by The Electrochemical Society. The bulk of the indexing activities were carried out over a 2-1/2 years span at the University of Illinois by some 90 students and professionals in about 25,000 hours of effort.7 Swann’s long-standing admiration for Prof. Fichter led to his decision to avoid duplication of the collection published earlier by Fichter8 since it was readily available. That decision represented an act of deep respect intended to preserve the importance of Fichter’s work. Swann however, included duplications of Fichter references that appeared in other languages and not cited by him, as well as many early references not reported by Fichter.

Over 12,000 citations were listed in the 755-page publication. The general guideline was that only compounds synthesized with a yield in excess of 10% qualified for incorporation—about 8,000 compounds were found. References were grouped into eight chapters according to the type of reaction involved (anodic, cathodic, organometallic electrolysis and synthesis, etc.), each of which was further divided into sections that indicated the type of chemistry involved (i.e., for anodic reactions: electrolysis of salts of organic acids, oxidative coupling, oxidative cleavage, etc.). Also included were books, reviews, laboratory manuals, and dissertations. Over half of the volume consisted of six indices that provide multiple routes by which relevant information may be retrieved. The work was published by The Electrochemical Society in 1980 and was available for purchase until the Society moved to its Pennington headquarters location.

Professor Sherlock Swann, Jr., was a truly gracious, old-school, Victorian, southern gentleman, and a scholar of the highest order. He passed away on March 14, 1983, and rests in the family plot on the highest hill overlooking the Greenmount Cemetery in Baltimore.

40

Prof. Sherlock Swann, Jr., electro-organic chemist and master bibliographer, seated in his office. The bookcases behind him contain volumes of the Transactions of The American Electrochemical Society from Volume 1 (1902) onward, with various titles, to the present time.

About the Author Richard Alkire studied chemical engineering at Lafayette College, the University of California at Berkeley, and the Max Planck Institut für Physikalische Chemie in Göttingen prior to joining in 1969 the faculty of the University of Illinois, where he is currently the Charles and Dorothy Prizer Chair Emeritus. He has directed the thesis research of 86 graduate students on topics of electrochemical engineering. His contributions have been recognized in numerous ways that include election to the U.S. National Academy of Engineering in 1988. He served as President of The Electrochemical Society in 1985-86.

References 1. F. M. Perkin, “Practical Methods of Electrochemistry,” Longmans, Green, London/New York, (1905).

2. E. Müller, “Electrochemisches Praktikum,” Th. Steinkopff, Dresden (1924).

3. S. Swann, Jr., “Annual Survey of American Chemistry, vol. 10, Chap. XI: Electro-organic Chemistry,” ed. C. J. West, National Research Council, p. 152-62 (1935), Reinhold, New York.

4. S. Swann, Jr., “Industrial Possibilities of Electro-organic Reductions,” Ind. Eng. Chem. 29, 1339-41 (1937).

5. Lav Arnin, “Bemerkungen über Volta’s säule. Zweiter brief.

Wirkungen der voltaischen säule auf vegetablische under animalische stoffe,” Ann. Physik 8, 257-70 (1801).

6. S. Swann, Jr., “Electrolytic Reactions”, in Technique of Organic Chemistry, Vol. III 2nd Ed., ed. A. Weissberger, Interscience, New York, p. 385-523 (1956).

7. “Bibliography of Electro-Organic Syntheses, 1801-1975,” Compiled by Sherlock Swann, Jr., and Indexed under Direction of Richard Alkire, The Electrochemical Society, Princeton, NJ, 755 pages, 12,062 references, 1980.

8. Fr. Fichter, “Organische Electro-chemie,” Th. Steinkopff, Dresden, 1942; Reprinted from Edwards Brothers, Ann Arbor, MI; Available from University Microfilms International, Ann Arbor, MI. The Electrochemical Society Interface • Winter 2014

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41

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The Electrochemical Society Interface â&#x20AC;˘ Winter 2014

T ECH HIGHLIGH T S Chloride Ion Interaction with Oxide-Covered Aluminum Leading to Pitting Corrosion Corrosion would be a much more common phenomenon were it not for the passive oxide film that forms on and protects the underlying metal. Instead, localized (crevice, pitting) corrosion commonly occurs through non-homogenous environments and through the action of aggressive anions such as the chloride ion. The authors of this review article recognized that many proposed mechanisms of Cl− interacting with the passive film, particularly those of aluminum, have been described, but no consensus has been reached by the research community. These authors embarked on summarizing what is known about the Cl− interactions with passive films on Al, and a couple of Al alloys. After quickly addressing the fact that Cl− is adsorbed by the positively charged surface of passive films typically having a potential of zero charge ~pH 9, the authors present experimental evidence for Cl− being incorporated into the passive film, being present below, as well as above the pitting potential. The authors assert that the body of evidence shows that Cl− incorporation occurs via ion migration and leads to reaction at the oxide/metal interface.

These reviewers add their interpretation of the data and present McCafferty’s stepwise model as the best explanation consistent with all experimental data.

From: J. Electrochem. Soc., 161, C421 (2014).

Modeling Volume Change due to Intercalation into Porous Electrodes Lithium-ion batteries are electrochemical devices whose performance is influenced by transport processes, electrochemical phenomena, mechanical stresses, and structural deformations. Many mathematical models already describe the electrochemical performance of these devices. Some models go further and account for changes in porosity of the composite electrode.

Other models focus on the coupled volume expansion and resulting stresses arising from the (de)lithiation process. Researchers from the University of South Carolina, in their article published in the JES Focus Issue on Mathematical Modeling of Electrochemical Systems at Multiple Scales, considered both of these factors in developing a model that accounts for stresses that build up in a porous electrode due to active material volume change. For their calculations, the authors assumed a 100% volume change in the active material component of the electrode coating.

The cell casing presented the bounds on the expanding electrode, ranging from rigid, non-compliant to flexible, compliant casing.

As expected, the volume change for the more rigid casing is accommodated by the porosity and consequently leads to increased ionic resistance. For the compliant casing, The Electrochemical Society Interface • Winter 2014

the volume change in the active material translates more into dimensional change.

The authors present their model results as a function of state of charge. Their equations can be incorporated into porous electrode theory for a more complete battery model and better understanding of battery performance and failure mechanisms.

From: J. Electrochem Soc., 161, E3297 (2014).

InZnSnO-Based Electronic Devices for Flat Panel Display Applications Thin film transistor (TFT) advances will play a key role in the system-on-panel (SoP) concept for driver, sensor, memory and other devices in compact displays. In flat panel display technology, TFTs with better pixel transmittance and low-power, reliable switching capabilities, are needed for SoP systems and circuitry. Higher mobility materials should offer enhanced transparency, electrical response and stability, and ease in processing. Advances in amorphous oxide materials offer the possibility of integrating resistive random access memory (RRAM) devices for non-volatile memory applications, and display panel integration in TFT form. In their report as part of the JSS Focus Issue on Oxide Thin Film Transistors, researchers at the National Chiao Tung University in Taiwan have demonstrated a versatile amorphous InZnSnO (a-IZTO) oxide semiconductor in TFT and RRAM technologies for SoP applications. When fabricated as a TFT device, the a-IZTO thin film exhibited a high field effect mobility of 39.6 cm2/V·s with enhanced electrical stability. The a-IZTO film also retained >80% transmittance in the visible frequency range. As a RRAM device, excellent resistive switching characteristics were observed over several hundred cycles.

A conceptual memory array architecture is postulated with each node comprising the a-IZTO TFT connected to one RRAM cell structure (1T1R). These high mobility oxide films are promising materials for low-cost technologies for integration into system-onpanel applications.

From: ECS J. Solid State Sci. Technol., 3, Q3054 (2014).

Superconformal Filling of Through Vias Through vias are useful in creating 3D integrated circuits and packages because they enable the fabrication of vertical interconnections through the substrate (typically silicon, sometimes glass). Here, electroplating processes can be used to fill the via with a conductive material such as copper.

Researchers at The State University of New York at Binghamton recently reported the results of a study on the use of plating inhibitors (chloride ion and tetranitroblue tetrazolium chloride, TNBT) to the superconformal filling of narrow (50 µm), high aspect ratio (AR=6) through-glass vias. The plating

solution was 0.88 M CuSO4 containing 40 ppm Cl− and 40 ppm TNBT. By optimal choice of other critical plating parameters (current density, time), the authors showed that via filling can be precisely controlled so it proceeds by the so-called “butterfly” plating mechanism, whereby the copper plating bridges across the diameter in the middle of the via. This effectively produces two blind vias that then fill very nicely as the plating process proceeds. Establishment of a concentration gradient of the Cl− and TNBT inhibitors leads to a substantially higher electrodeposition rate in the middle of the via compared to rates at the flat surface or at the via openings; therefore, there is only minimal copper deposition produced on the surface during the via fill, which is desirable.

From: ECS Electrochem. Lett., 3, D30 (2014).

Nanoparticle-Carbon Nanofiber Composites for Pt-Free Dye-Sensitized Solar Cells Over the past few decades, dye-sensitized solar cells (DSSCs) have been actively studied given their promise of reasonable efficiency, fabrication costs, and environmental friendliness. One route to making DSSCs more economical is decreasing or eliminating the amount of Pt used in the counter electrode. Researchers in Korea investigated the use of a TiO2 nanoparticle-carbon nanofiber (CNF) composite as an alternative catalyst at the counter electrode. Three composites containing different amounts of nitrogen-doped TiO2 were synthesized using electrospinning. Complete DSSCs were fabricated, characterized, and tested for their performance. The highest weight percent sample (13.8 wt%) investigated gave the highest values for the metrics of photocurrent density (15.65 mA/cm2), fill factor (60.5%), and power-conversion efficiency (6.31%).

Each of these values comparably matched or slightly exceeded those for the Pt counter electrode sample. The authors speculated that the combination of high surface roughness of the TiO2 particles on the CNFs and the decreased charge transfer resistance stemming from the highly catalytic TiN phases resulted in enhanced reduction of I3- at the counter electrode. This work demonstrated a cheaper DSSC, with improved performance, using a TiO2-CNF composite.

From: ECS Solid State Lett., 3, M33 (2014).

Tech Highlights was prepared by Mike Kelly of Sandia National Laboratories, Colm O’Dwyer of University College Cork, Ireland, and Donald Pile of Nexeon Limited. Each article highlighted here is available free online. Go to the online version of Tech Highlights, in each issue of Interface, and click on the article summary to take you to the full-text version of the article.

43

ECS is proud to announce the establishment of the

Allen J. Bard Award in Electrochemical Science Award recipients will be honored for exceptional contributions to the fields of fundamental electrochemical science and recognized for exceptionally creative experimental and theoretical studies that have opened new directions in electroanalytical chemistry and electrocatalysis.

The first award will be given in Chicago at the 227th ECS Meeting.

Allen J. BArd is the Norman Hackerman-Welch Regents Chair in Chemistry in the Department of Chemistry at The University of Texas at Austin, and the Director of the Center for Electrochemistry.

Allen J. BArd

Among Dr. Bard’s many awards are The Electrochemical Society’s Carl Wagner Memorial Award (1981), Henry B. Linford Award for Distinguished Teaching (1986), and Olin Palladium Award (1987); Priestley Medal (2002), the Wolf Prize in Chemistry (2008). He was elected into the American Academy of Arts & Sciences in 1990. In 2013, Dr. Bard was awarded the National Medal of Science, one of the highest honors bestowed by the U.S. government upon scientists, engineers, and inventors.

Special thanks to the generous support of our donors and advertisers, especially:

CH Instruments We need your help to ensure the award is fully funded in perpetuity , and we may also create a symposia in Dr. Bard’s honor.

To help fund the award endowment and a continuing symposium in Dr. Bard’s honor, please donate online:

electrochem.org/bard

Numerical Modeling for Corrosion

by Shinji Fujimoto

T

he ECS Corrosion Division was established in 1942 to organize and promote discussions associated with the behavior of materials in environments that cause corrosion, oxidation, and related surface reactions. This Division provides a forum for scientists and engineers to meet and discuss common problems in the hope of advancing research, education, and training in this important field.

Over the years, a number of the members of the Corrosion Division have served as ECS President, including H. H. Uhlig, N. Hackerman, F. L. LaQue, D. A. Vermilyea, T. R. Beck, R. C. Alkire, R. P. Frankenthal, W. H. Smyrl, B. MacDougall, and P. M. Natishan. Over the past seven decades, the Division has sponsored numerous corrosion related symposia and organized the Corrosion Monograph series of books that outline and review many areas of corrosion science and engineering.

The Corrosion Handbook, originally edited by H. H. Uhlig in 1946 (its 3rd edition was revised by R. Winston Revie in 2011), remains one of the most popular corrosion reference books worldwide.

In this issue, we present four articles related to numerical approaches to corrosion science and engineering. Corrosion damage of equipment, production facilities, and infrastructure has severe consequences, including loss of property, interruption of production and transportation, and outage of electricity, water, and gas supplies.

Such disruptions occur at a very high cost to society. While it is difficult to estimate the direct economic loss due to corrosion damage, the expense incurred to avoid/prevent corrosion damage, i.e., â&#x20AC;&#x153;corrosion cost,â&#x20AC;? has been estimated for several economies, including that of the U.S.,1 Japan,2 and the EU.3 The corrosion cost is invariably high, at a few percentage points of GDP annually (3.1% of GDP in the U.S.1).

To minimize corrosion cost, a large amount of effort has been expended to facilitate prediction of corrosion damage. To accurately predict corrosion events, it is necessary to establish high-quality numerical models for a wide range of very complicated corrosion phenomena. In the decade from 1970 to 1980, numerical calculations mainly used finite element methods (FEM) and yielded deterministic models for the study of localized corrosion.4,5 Such studies contributed to the fundamental understanding of the mechanisms of localized corrosion, but were not necessarily practical for actual corrosion prediction. Subsequently, stochastic or probabilistic models6 were developed based on the distribution of the (corrosion-induced) failure time in the laboratory and/or in the field. These approaches introduced high-level statistics and other mathematical methods in conjunction with accumulated field data, and were successful in predicting localized corrosion phenomena, such as pitting corrosion and stress corrosion cracking experienced in process industries.7 To predict corrosion damage for new combinations of materials and environments, the stochastic and probabilistic approach is not necessarily effective, and deterministic models are required. Recent improvements in and development of computing technologies and calculation methods, including first principle calculations, have enabled advanced numerical modeling of corrosion phenomena as a combination of electrochemistry, solution chemistry, mass transfer, and atomistic process.

The four articles in this issue provide both an historical outline and recent developments in numerical corrosion modeling. Liu and Kelly review the fundamental numerical modeling of localized corrosion by electrochemistry and mass transfer using FEM, and introduce their recent results adopting a commercial FEM package with electrochemical modules.

The article by Amaya, Yoneya, and Onishi describes a practical corrosion prediction method for large-scale structures, such as the cathodic protection of the hull of a ship and large ocean structures using the boundary element method. The introduction of the inverse analysis method based on Bayesian estimation enables the study of large-scale structures by combining numerical calculations with infield monitoring of parameters such as the corrosion potential.

The Electrochemical Society Interface â&#x20AC;˘ Winter 2014

The article by Tylor reviews the most recent ab initio calculations on corrosion processes at the atomistic scale and introduces approaches pertaining to molecular design of corrosion inhibitors, chemisorption of molecules and ions on metals or surface passive films that are closely related to corrosion, and characterization of the structure of the metal/oxide interface.

Finally, the article by Laycock, Krouse, Hendy, and Williams addresses both the deterministic model and the stochastic model. The authors attempt a full description of the pitting corrosion process, including initiation and propagation, on stainless steel in an attempt to develop a reliable predictive model for industrial applications.

The articles in this issue review the current validity and future possibilities pertaining to the prediction of corrosion by numerical modeling. Recently, in the area of materials science, the concept of the Materials Genome has been launched, where comprehensive approaches encompassing experimental and numerical simulation are recognized to be significant. The typical corrosion scientist is well versed in experimental work, but perhaps not so much in modeling.

If this issue provides the requisite introductory guidance to numerical modeling of corrosion, the authors would be very pleased!

About the Author Shinji Fujimoto is the Past Chair of Corrosion Division. He is currently a Professor in the Division of Materials and Manufacturing Science, Graduate School of Engineering, Osaka University, Japan. He graduated from Osaka University, and obtained Dr. Eng. degree in Metallurgical and Materials Engineering from Osaka University in March 1987. Immediately afterwards, he joined the Metallurgy and Materials Engineering Department (currently Division of Materials and Manufacturing Science), Osaka University. He was appointed to the position of Professor of Environmental Materials in 2002. He stayed at the Corrosion and Protection Centre of UMIST, Manchester, UK in 1991-1992 as a Research Associate. His research interests are corrosion science and engineering, including passivity, localized corrosion, surface modification and electrochemical characterization of metallic biomaterials. He may be reached at fujimoto@mat.eng.osaka-u.ac.jp.

References 1. G. H. Koch, M. P. H. Brongers, N. G. Thompson, Y. P. Virmani, and J. H. Payer, Corrosion Costs and Preventive Strategies in the United States, NACE, Houston, TX (2012). Available at http:// www.nace.org/Publications/Cost-of-Corrosion-Study/.

2. Committee on Cost of Corrosion of Japan Society of Corrosion Engineering, Cost of Corrosion in Japan, Zairyo-to-Kankyo, 50, p.490 (2001). English translation available at http://www.nims. go.jp/mits/corrosion/corrosion_cost.pdf.

3. http://www.iom3.org/content/society-board-31.

4. H. W. Pickering and R. P. Frankenthal, On the Mechanism of Localized Corrosion of Iron and Stainless Steel: I. Electrochemical Studies, J. Electrochem. Soc., 119, 1297 (1972).

5. J. R. Galvele, Transport Process and the Mechanism of Pitting of Metals, J. Electrochem. Soc., 123, 464 (1976).

6. T. Shibata and T. Takeyama, Stochastic Theory of Pitting Corrosion, Corrosion, 33, 243 (1977).

7. Proceedings of the International Symposium on Plant Aging and Life Prediction of Corrodible Structures, Ed. by T. Shoji and T. Shibata, NACE, Houston, TX (1997).

45

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46

The Electrochemical Society Interface • Winter 2014 11/12/14

The Use of Finite Element Methods (FEM) in the Modeling of Localized Corrosion

by C. Liu and R. G. Kelly

L

ocalized corrosion is characterized by intense dissolution at discrete sites on the surface of a metal or alloy, while the remainder of the surface corrodes at a much lower rate. The ratio of the two rates is on the order of 109. Typical forms of localized corrosion include crevice corrosion, pitting, stress corrosion cracking, and intergranular corrosion.1 Localized corrosion represents the primary corrosion failure mode for passive/corrosion resistant materials.

There has been extensive experimental characterization of the dependence of the susceptibility to corrosion on alloy and solution composition, temperature, and other variables. Computational modeling can play an important role in improving the understanding of localized corrosion processes, in particular when it is coupled with experimental research that accurately quantifies the important characteristics that control corrosion rate and resultant morphology.

There are many modeling methods that can be applied, with the choice of method driven by the goal of the modeling exercise.

Empirical models2 can be used to predict performance within the parameter space for which they are created. Such models can provide insight into what kinds of processes might be dominating the corrosion process, but further dissection of controlling factors is more difficult.

Numerical modeling, in which the concentration, potential, and current distributions are calculated, plays a role in helping to understand controlling factors. There are several numerical methods that have been implemented by corrosion scientists and engineers.

Among these, the finite element method (FEM) has been the most widely used to investigate transport phenomena in systems undergoing.

The finite element method (FEM) is a numerical technique used to obtain approximate solutions to the differential equations that describe a wide variety of physical phenomena, ranging from electrical and mechanical systems to chemical and fluid flow problems. Generally, FEM establishes credible stability criteria and provides more flexibility (e.g., in handling inhomogeneity and complex geometries) compared to other numerical modeling methods such as the finite difference method (FDM). The finite element approach in corrosion study was introduced in the early 1980s by Alkire, Forrest, and Fu.3-5 The FEM approach has demonstrated an ability to predict electrochemical parameters such as potential and current distributions for localized corrosion.

FEM Modeling in Localized Corrosion In the general case, the Nernst-Planck Equation, suitable for dilute solutions, is applied as the governing equation in FEM modeling for localized corrosion. The basic form6 of this equation can be formulated as

Diffusion

Migration

(1)

Convection Reaction

where ci is the concentration of species i, Di is the diffusivity of species i, zi is the charge of species i, F is Faraday’s constant,  is the electric potential, v is the fluid velocity, and Ri is rate of homogeneous production of species i. In general the convection term is neglected in localized corrosion modeling, although Harb and Alkire7 have shown the conditions under which convection at the mouth of a pit

can influence the conditions inside the pit. A common assumption in mathematical modeling of transport phenomena in electrochemical systems is electroneutrality

(2)

Electroneutrality states that any volume of solution is electrically neutral due to the large restoring force resulting from any separation of charge.

The solution to the Nernst-Planck equation results in full transient descriptions of the distributions of chemical composition, potential, and current density. The costs of obtaining this complete data set are computational complexity and time. The wide range of time scales that must be taken into account in modeling localized corrosion include very fast processes (ion reaction and response to potential gradients) and slow processes (diffusion of uncharged species under a concentration gradient). This range of timescales, combined with the mathematical difficulties in dealing with highly nonlinear boundary conditions (electrochemical kinetics) make the calculations very difficult, requiring very small time steps and highly refined spatial meshing.

Recent work8-12 has shown the usefulness of the application of the Laplace Equation (Eq. 3) to model steady state current and potential distributions under thin-electrolyte conditions.

   0 2

(3)

Rather than solving for the full transient, the use of the Laplace Equation approach relies instead on a knowledge or estimation of the electrolyte characteristics (primarily conductivity) and its dependence on position and other experimental variables. This approach ignores diffusive transport contributions to the current density. It has been shown that reasonable estimations of important characteristics of the thin electrolytes forming under atmospheric conditions can be made based on a limited number of measurements and equilibrium calculations. Accurate measurement of the electrochemical kinetics is far more important in determining the success of the model predictions.

Below, two explicit examples regarding applications of FEM in localized corrosion modeling using the simplification of the Laplace equation are presented. The first example presents the use of FEM modeling to predict intergranular corrosion (IGC) damage caused by galvanic interactions in a thin electrolyte. The second example describes a FEM-based model combined with rigorously controlled crevice geometry for the study of crevice corrosion scaling factors.

FEM Modeling to Predict IGC Damage Caused by Galvanic Interactions10 In experimental work, Mizuno and Kelly13 quantitatively investigated the galvanic interaction between sensitized aluminum alloy AA5083-H131 and AISI 4340 steel for samples exposed to a variety of atmospheric and full immersion conditions. A linear correlation was found between the maximum depth of IGC damage and the electrochemical potential under full immersion conditions.

Scanning Kelvin Probe measurements of the potential along a galvanic couple of AA5083-H131 and 4340 steel exposed to a thin electrolyte layer were made to demonstrate that the same potential dependence applied to atmospheric conditions.13 However, it is (continued on next page)

The Electrochemical Society Interface • Winter 2014

47

Liu and Kelly

(continued from previous page)

(a)

Fig. 1. Geometry in FEM Model representative of a galvanic couple between AA5083-H131 and AISI 4340. Water layer thickness determined by relative humidity (RH) and loading density (LD) of salt according to Chen, et al.14

difficult to comprehensively measure potential distributions during atmospheric corrosion because many environmental factors affect IGC propagation. Computational modeling can be utilized to simulate potential distribution in the corrosion system, and IGC propagation can be predicted from the simulated potential distributions under atmospheric conditions.

The geometry used is shown in Fig. 1, representing a galvanic couple that occurs when a 4340 steel fastener is coupled with sensitized AA5083-H131. The Nernst-Planck equation was used as the governing equation as implemented in a commercial computational code, and the boundary conditions used were based on electrochemical kinetics parameters fitted to the Bulter-Volmer equations from experimentally determined polarization curves.13 The calculations were made for t = 0, preventing any solution chemistry change or diffusion from occurring. Thus, the governing equation was effectively the Laplace equation. Optimization of the boundary conditions was performed to reproduce the observed galvanic corrosion behavior as a function of degree of sensitization (DoS) and NaCl concentration.

The calculated potential distribution was converted to the IGC depth using the correlation determined from the full immersion testing.13 Fig. 2 presents an example of the comparison of the IGC depth distributions between the model calculations and experimental results. Although the experimentally observed IGC depth had significant variability even at the same distance from the steel fastener, the calculations showed IGC distributions very similar to those of the experiments for the entire range of DoS. In addition to reasonably predicting the depth of attack, the modeling predicted with reasonable accuracy the maximum distance from the steel at which IGC damage was observed.

The utility of FEM modeling is shown in Fig. 3, where the calculated maximum IGC depth as a function of RH for these DoS levels is presented. The modeling allows rapid exploration of the effects of the range of important variables. We can gather that the most severe attack is expected to occur at approximately RH = 90% for all DoS levels, that the minimally sensitized specimen (DoS=10 mg/cm2) is not susceptible to IGC when the RH is higher than 95% or lower than 80%, and that the influence of DoS on maximum IGC depth saturates above a DoS of 40 mg/cm2. Such FEM-based models can be used to guide experiments and to provide inputs for predicting lifetime and maintenance requirements for structures of interest.

(b)

(c)

FEM Modeling Combined with Rigorously Controlled Crevice Geometry for Study of Crevice Corrosion Scaling Law15 Historically, one of the major challenges in crevice corrosion research has been the disconnect between the crevice geometries that can be modeled and those that can be attained experimentally.

This situation led to a sharp disagreement about how the crevice gap controls the position of maximum attack within the crevice, even for simple electrochemical systems in which the experiment is arranged to prevent any solution composition change within the crevice.16 The relation between the position of maximum attack (xcrit) and the crevice gap (G) is known as the scaling law. Two distinct scaling laws 2 for crevice corrosion had been suggested, xcrit /G16, 17 and xcrit /G.16 48

Fig. 2. Comparison of the IGC damage derived from the calculated potential distributions and the experimentally determined IGC damage after 100 h: (a) DoS = 10 mg/cm2; (b) DoS = 30 mg/cm2; (c) DoS = 50 mg/cm2. In all cases, the LD was 3.5 DoS = 3.5 g/m2.10

The Electrochemical Society Interface • Winter 2014

A comparison of xcrit data from the crevice corrosion experiments and those predicted by the model is shown in Fig. 6a. Figure 6b plots the same data, but with the 2 ordinate now in terms of xcrit . At small gaps (< 100 μm) the data fit to a linear regression has a correlation coefficient of 0.9957 with the y intercept forced through zero. From these comparisons, it was concluded 2 that a quadratic scaling factor (xcrit /G = constant) was applicable to the Ni/H2SO4 crevice system, with the result most apparent at short times and small gaps. The model also reproduced the experimentally observed failure of the scaling law at large gaps where the xcrit was located at much greater depths than would be expected from the scaling law. The potential and current distributions explain this observation. At the 153 μm gap crevice, the entire active/passive transition was not completed before the end of the crevice was reached, thus reducing the total current from the crevice and the subsequent potential drop.

State-of-Art Issues in Localized Corrosion Modeling Application of numerical methods, especially FEM, has greatly facilitated understanding phenomena and Fig. 3. Model calculation results for maximum IGC propagation after 100 h exposure as a mechanisms across a diverse spectrum of localized function of RH (DoS = 0 to 50 mg/cm2, LD = 3.5g/m2).10 corrosion problems. However, important issues still remain in localized corrosion modeling that hinder comparisons of modeling results and experimental data. Most of the The objective of the work in this example was to unambiguously issues are rooted in assumptions and simplifications that are made in assess which scaling law applies, particularly to small crevices. Lee, order to make the calculations more tractable.

Reed, and Kelly15 combined FEM modeling and microfabrication One important issue comes from ignoring ion-ion interactions methods to rigorously link computational results with experimental in the electrolyte. Generally, modeling of the ion transport process measurements. Microfabrication methods were used to construct is based on the assumption of dilute solution conditions, and the crevice formers of rigorously controlled dimensions. These formers Nernst-Planck equation is used as discussed to describe ion transport were used in crevice corrosion experiments on Ni200 in 0.5 M due to diffusion, migration, and convection. For the migration term, H2SO4 to measure xcrit for crevice gaps of 14, 35, 93, 153, and 395 the flow of each ion due to electric potential field in the system is μm. Comparison of the modeling and experimental results provided assumed to be independent. However, the electric potential field is a better understanding of the geometric scaling factors that apply to also affected by distribution of all the ions as described by Poisson’s crevice corrosion. equation which accounts for the relationship between charge The FEM program used in this work was capable of considering densities and the electric potential two spatial dimensions and time,17,18 as in the earlier example, convection was ignored, and the potential and current distributions

(4) were calculated at t = 0, effectively reducing the governing equation to the Laplace equation. The geometry used is shown in Fig. 4. The fit The rigorous approach to model transport phenomena in dilute to the potentiodynamic scan of Ni200 in sulfuric acid (which contains solution environment is to solve the Nernst-Planck equation coupled an active/passive transition) served as the electrochemical boundary with the Poisson's equation. However, attempts to obtain numerical condition for the model. solutions by applying these two equations have encountered The potential and current density distributions obtained from the substantial numerical stiffness19 when performing calculations. Thus, FEM model are shown in Fig. 5. The potential fell monotonically with the more widely used approach invokes electroneutrality, which increasing distance into the crevice, and the corresponding dissolution ignores electrostatic interaction between ions, as a replacement for current density mapped out the passive-to-active transition. The xcrit Poisson’s equation to describe ion transport in the electrochemical value for each gap was determined by locating the position at which system. However, this coupling of the Nernst-Planck equation with an the potential fell into the active region bounded at +0.244 V (vs. SCE). electroneutrality assumption loses sight of the fundamental physics.

The basic form of the Nernst-Planck equation shown in Eq. 1 ignores ion-ion interactions. In practice, to use the Nernst-Planck equation in combination with the electroneutrality condition, at each time step for each spatial element, a “make-up” ion is selected to enforce Crevice Tip electroneutrality. There is concern that this lacks a defendable x=L physical basis, particularly when it is not obvious which ion should L be selected. In some cases, negative concentrations can be predicted.

Several approaches have been proposed to take into account ionion interactions during ion transport in dilute solutions. Heppner x = xcrit and Evitts21 developed a charge density correction method based on Poisson’s equation to calculate the effect of charge density on Crevice Mouth G electrolyte mass transport. By using an operator splitting method,22,23 x=0 the value of a charge density correction can be determined to offset the charge of the electrolyte solution. Sarkar and Aquino20 developed Fig. 4. Schematic diagram illustrating the important parameters of crevice corrosion scaling laws.15 The Electrochemical Society Interface • Winter 2014

(continued on next page) 49

Liu and Kelly

Concluding Comments

(continued from previous page)

a novel finite element approach to describe the mass transport process in dilute solutions with the consideration of ion-ion interactions. They incorporated Onsager’s approach24,25 in which the total flux of an ion is a linear combination of all the thermodynamics driving forces, but assumed that the ion distributions in the electrochemical system are independent, neglecting the cross-coefficients in Onsager’s formulation.20 In their approach, a new thermodynamic parameter was defined, which can be interpreted as the rate of accumulation of one ion species at a local point in the domain due to ionic interactions.

This parameter was then included in the Nernst-Planck equation, creating a modified mass transport equation. By solving the system of modified mass transport equations for all involved ion species, the electroneutrality condition, and Poisson’s equation at the same time, the concentration and potential distribution profiles were calculated.

Later, Sarkar and Aquino26 applied this approach20 to simulate the movement of a pit surface, as well as the time-dependent profiles of concentration, current, and potential distribution inside the pit.

(a)

FEM analyses have contributed a great deal to our understanding of localized corrosion conditions, including identification of key parameters. The availability of commercial FEM codes with electrochemical modules allow non-experts to input geometries, boundary conditions, and initial conditions. This development will no doubt increase the use of FEM for these studies. Further fundamental work is still needed, though, to address the effects of often implicit assumptions.

Acknowledgments We wish to thank the Office of Naval Research (ONR) for its financial support through Grant N00014-14-1-0012. William Nikerson, Technical Office, is gratefully appreciated.

(b)

Fig. 5. (a) Potential distributions estimated by the model for gaps ranging from 14 to 395 μm. (b) Corresponding current density distributions for each gap.15

(a)

(b)

Fig. 6. (a) Comparison of experimental and computational data for xcrit for Ni200 in 0.5 M H2SO4 as a function of gap plotted on linear scales for both xcrit and gap. (b) Comparison of experimental and computational data of xcrit for Ni200 in 0.5 M H2SO4 as a function of gap plotted on a quadratic scale for xcrit and a linear scale for gap.15 50

The Electrochemical Society Interface • Winter 2014

About the Authors

References

Chao Liu is a graduate research assistant supervised by R. G. Kelly in the Department of Materials Science and Engineering at the University of Virginia. His research mainly focuses on mathematical modeling of localized corrosion under atmospheric conditions. He serves on the executive board of the ECS student chapter at the University of Virginia and is also a student member of NACE International. He obtained his Bachelor’s degree in applied chemistry from Nanchang University, China, and completed his Master’s study in chemical engineering under M. E. Orazem at the University of Florida. He can be reached at cl5bc@virginia.edu.

1. D. A. Jones, Principles and Prevention of Corrosion, 2nd ed., Prentice-Hall, Inc., Upper Saddle River, NJ ( 1996).

2. M. L. C. Lim, J. R. Scully, and R. G. Kelly, Corrosion, 1, 35 (2013).

3. R. Alkire, T. Bergh, and R. L. Sani, J. Electrochem. Soc., 125, 1981 (1978).

4. A. W. Forrest Jr., J. W. Fu, and R. T. Bicicchi, Paper 150 presented at the NACE National Conference, Chicago, March, 1980.

5. J. W. Fu, Paper 115 presented at the NACE National Conference, Toronto, April, 1981.

6. J. Newman, and K. E. Thomas-Alyea, Electrochemical Systems, 3rd ed., Wiley-Interscience, Hoboken, N. J (2004).

7. J. N. Harb, and R. C. Alkire, J. Electrochem. Soc., 138, 3568 (1991).

8. F. Cui, F. J. Presuel-Moreno, and R. G. Kelly, Corrosion, 62, 251 (2006).

9. F. J. Presuel-Moreno, H. Wang, M. A. Jakab, R. G. Kelly, and J. R. Scully, J. Electrochem. Soc., 153, B486 (2006).

10. D. Mizuno, and R. G. Kelly, Corrosion, 69, 681 (2013).

11. M. Verbrugge, Corros. Sci., 48, 3489 (2006).

12. G. L. Song, Adv. Eng. Mater., 7, 563 (2005).

13. D. Mizuno, and R. G. Kelly, Corrosion, 69, 580 (2013).

14. Z. Y. Chen, F. Cui, and R. G. Kelly, J. Electrochem. Soc., 155, C360 (2008).

15. J. S. Lee, M. L. Reed, and R. G. Kelly, J. Electrochem. Soc., 151, B423 (2004).

16. Y. Xu, and H. W. Pickering, J. Electrochem. Soc., 140, 658 (1993).

17. L. A. DeJong, M. S. Thesis, Department of Materials Science and Engineering, University of Virginia, Charlottesville, VA (1999).

18. K. C. Stewart, Ph.D. Dissertation, Department of Materials Science and Engineering, University of Virginia, Charlottesville, VA (1999).

19. S. W. Feldberg, Electrochem. Commun., 2, 453 (2000).

20. S. Sarkar, and W. Aquino, Electrochim. Acta, 56, 8969 (2011).

21. K. L. Heppner, and R. W. Evitts, Corros. Eng., Sci. Technol., 41, 110 (2006).

22. R. W. Evitts, Ph.D. Dissertation, University of Saskatchewan, Saskatoon, Saskatchewan, Canada, (1997).

23. M. K. Watson, Ph.D. Dissertation, University of Saskatchewan, Saskatoon, Saskatchewan, Canada, (1989).

24. L. Onsager, Phys. Rev., 37, 405 (1931).

25. L. Onsager, and R. M. Fuoss, J. Phys. Chem., 36, 2689 (1932).

26. S. Sarkar, J. E. Warner, and W. Aquino, Corros. Sci., 65, 502 (2012).

R. G. Kelly is the AT&T Professor of Engineering in the Department of Materials Science and Engineering at the University of Virginia, whose faculty he joined in 1990. His present work includes studies of the electrochemical and chemical conditions inside localized corrosion sites, atmospheric corrosion, improved accelerated testing, and multi-scale modeling of corrosion processes. He is the CoDirector of the Center for Electrochemical Science and Engineering at UVa. He is a Fellow of ECS as well as NACE International. He completed his PhD studies at the Johns Hopkins University under Patrick Moran, Eliezer Gileadi, and Jerome Kruger. He then spent two years at the Corrosion and Protection Centre at the University of Manchester (UK) as a Fulbright Scholar and as an NSF/NATO Post-doctoral Fellow working with Roger Newman. He can be reached at rgkelly@virginia.edu.

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The Electrochemical Society Interface â&#x20AC;˘ Winter 2014 1

Obtaining Corrosion Rates by Bayesian Estimation: Numerical Simulation Coupled with Data

by Kenji Amaya, Naoki Yoneya, and Yuki Onishi

P

rotecting structures from corrosion is one of the most important challenges in engineering. Cathodic protection using sacrificial anodes or impressing current from electrodes is applied to many marine structures. Prediction of the corrosion rates of structures and the design of cathodic protection systems have been traditionally based on past experience with a limited number of empirical formulae.

Recently, application of numerical methods such as the boundary element method (BEM) or finite element method (FEM) to corrosion problems has been studied intensively,1-8 and these methods have become powerful tools in the study of corrosion problems.23-24 With the progress in numerical simulations, “Inverse Problems” have received a great deal of attention. The “Inverse Problem” is a research methodology pertaining to identifying unknown information from external or indirect observation utilizing a model of the system, as shown in Fig. 1.

The background of inverse problems is the modeling and simulation of natural phenomena. When observations are taken of these phenomena, the observation data are used to infer knowledge about physical states. One of the most spectacular successes in the field of inverse problems was the invention of an inversion algorithm for computed tomography by Cormack (1963) and its experimental demonstration by Hounsfield (1973). The two shared the Nobel Prize in Physiology/Medicine in 1979. Applications of inverse problems arise in many fields of engineering as well. In the field of corrosion engineering, there are many issues that benefit from an inverse analysis approach.

In this article, the use of numerical simulation for evaluating corrosion rates is explained with the boundary element method as an example. Then, an inverse analysis method for identifying corrosion rates or cathodic protection currents from the (easily measured) potential distribution around marine structures is introduced. This method is based on the Bayesian estimation, with the measured data and numerical simulation focused on the potential distributions around a seaside structure.

Electrochemical Aspects and Mathematical Model We consider a typical metal M in an electrolyte. Both anodic and cathodic reactions occur simultaneously on the metal surface according to

Anodic reaction: M → M

n

ne

(1)

1   (2) Cathodic reaction: 2 O2 + H2O + 2e → 2OH Due to these reactions, an electric current flows. The density of the electric current across the metal surface (i) versus electrical potential in the electrolyte near the metal surface against a reference electrode, e.g., saturated calomel electrode (SCE) – (E) curve is called a polarization curve, which is schematically shown in Fig. 2. The relationship between the current density (i) and the potential E for anodic and cathodic reactions (solid curves) are not obtained individually; only the nominal relationship E = f(i) for the two reactions (dashed curve) are measured.

In the natural state, the reactions become balanced at point C in Fig. 2, and the current corresponding to CD flows from the anode to the cathode. The corrosion rate is proportional to this anodic current density CD. It is possible to suppress the anodic current density by impressing a current onto the metal through the electrolyte using an external power supply, or by connecting the metal object with a The Electrochemical Society Interface • Winter 2014

more base metal, i.e., sacrificial anode, and reducing the potential of the metal to the critical value Ep. This method is called cathodic protection (CP).18 We assume that the surface of the electrolyte domain Ω is surrounded by Γ(Γd + Γn + Γm) as shown in Fig. 3, where Γm is the metal surface, and the potential and current densities are prescribed on Γd and Γn, respectively. The potential field in the homogeneous electrolyte can be modeled mathematically by the Laplace’s Eq. 3 under boundary conditions Eq. 4 through Eq. 6 8

∇2φ = 0

φ = φ0 on Γd

(3) (4)

i (≡ κ ∂φ ) = i0 on Γn (5) ∂n -φ = f(i) on Γm (6)

where κ denotes the conductivity of the electrolyte, and ∂/∂n the outward normal derivative.

Note that the potential φ is defined with reference to the metal and has an inverse sign to that usually employed in corrosion problems, wherein the potential is defined against a reference electrode such as SCE. φ0 and i0 are the prescribed values of the potential and the current density, respectively. The function f(i) is the experimentally determined polarization curve as stated above. In case the corroding structure consists of multiple materials, the number of polarization curves is the same as that of the material types.

By solving Eq. 3 under the boundary conditions Eq. 4-6, the potential near the metal surface and the current density that is proportional to the corrosion rate can be determined. Because the knowledge of physical quantities on the metal surfaces is important, a boundary element method in which only the surface of analytical domains must be discretized with elements is employed here. The standard boundary element procedures19-20 lead to ϕ0 id

ϕn [G] i0  0 κ[H] (7) f(im) im where the detailed expressions of matrices, [H] and [G], are given in References 19 and 20 and the subscripts d, n, and m represent the quantities on Γd, Γn, and Γm, respectively. The system of nonlinear algebraic equations, Eq. 7, is solved by using an iterative procedure, e.g., the Newton-Raphson method.21 An experimental verification of the boundary element solution is shown in References 8 through 22. (continued on next page)

Fig. 1. Concept of inverse problems.

53

Amaya, Yoneya, and Onishi (continued from previous page)

Inverse Problem Approach As described above, the corrosion rate of a structure can be estimated by solving Laplace’s equation with nonlinear boundary conditions, which ůƵŵŝŶƵŵ ŶŽĚĞ are based on experimentally determined electrochemical polarization curves.

W ĐƵƌƌĞŶƚ However, the electrochemical polarization curves of the materials considered are not available in most practical cases. In such a case, the inverse approach, in which the current density on the surface of a metal structure is estimated from the measured Fig. 2. Schematic view of polarization curve. potential in the electrolyte, is necessary.

This type of inverse problem will be discussed here.

As shown in Fig. 4, the boundary and supplementary conditions to be treated in the inverse problem are given by

φ  φ0 on Γd i (≡ κ ∂ϕ) = i0 on Γn ∂n

ϕ = ϕ̄ on Γs

ϕ = fm (i;αj) on Γm

ϕ0 i ϕ [G] i0  0 f(i; αj) i

(10)

(11)

(12)

By considering a set of initial values of the parameters αj as the unknown or latent variables in the inverse problem, the following observation equation can be calculated by solving the direct problem Eq. 12

ϕs = h(αj )  v

(13)

where ϕs is the vector containing the value of potential at measurement points, and h( ) is the vector model function which represents the relationship between αj and ϕs. Also, v is a random variable vector corresponding to measurement noise and model error in the potential.

54

Ϭ

ŶŽĚĞ

Ɖ

I

݅ ൌ ݅௡ Ȟ௡

(9)

߶ ൌ ߶ௗ Ȟௗ

ȳ ‫׏‬ଶ ߶ ൌ Ͳ

߶ ൌ െ݂ሺ݅ሻ Ȟ௠

Fig. 3. Governing equation and boundary conditions.

where αj (j  1, 2, ..., L; L = total number of parameters) is a parameter in the function. Then, the many parameters in the function are estimated by an inverse analysis. After obtaining the polarization characteristics, the potential distribution is easily calculated by direct analysis.

Following the usual boundary element formulation with given boundary conditions, we obtain κ[H]

ĂƚŚŽĚĞ

(8)

In the inverse analysis, the boundary conditions of domain Ω are not fully given, but the value of potential can be obtained at several points in the electrolyte by practical measurement to compensate for this lack of boundary conditions. However, even if the number of the measured potential datapoints is increased sufficiently to permit solving the inverse problem, the solution would be abnormally unstable due to the ill-posed problem.25 Hence, we make use of the a priori information that ϕ and i on Γm must satisfy the polarization characteristics.26 At first, we approximate the polarization curve by a function, e.g., the Tafel expression27

݅ ൌ ݅௡ Ȟ௡ ߶ ൌ ߶ௗ Ȟௗ

߶ ൌ ߶ത௦ ȳ ‫׏‬ଶ ߶ ൌ Ͳ ߶ǡ ݅ǣ ‫ ݊ݓ݋݊݇݊ݑ‬Ȟ௠

Fig. 4. Governing equation and boundary conditions for inverse problem.

The Electrochemical Society Interface • Winter 2014

The inverse problem identifying the corrosion rate can be formulated as a maximum likelihood estimation (MLE) by regarding Îąj as random variables, whose solution can be obtained by

ÎąĚ&#x201A; j = arg min{î&#x20AC;˛ln p (Ď&#x2022;Ě&#x201E; s | Îąj )} Îąj

(14)

= arg min{î&#x20AC;˛ln pv (Ď&#x2022;Ě&#x201E; s î&#x20AC;˛ h(Îąj ))} Îąj

(15)

where, pv( ) is the probability density function of v, and Ď&#x2022;sĚ&#x201E; is the vector containing the measured potential data. This optimization calculation is repeated by modifying the parameters employing a minimizing technique, e.g., the conjugate gradient method. Even if the above procedure is followed, the solution for Îąj is sometimes unstable and it depends on the assumed initial values. In such a case, the Bayesian Estimation approach, which utilizes a priori information, is sometimes effective. For example, the a priori information could be that if the metal structure of interest is made of a low alloy steel, then the parameters of the polarization characteristics curve Îąj must be within some range. This kind of information is often available in engineering problems. Such information is easily expressed in the form of fuzzy membership functions pm(Îąj).27 The Bayesian Estimation solution can be formulated as ÎąĚ&#x201A; j = arg min{î&#x20AC;˛ln p (Ď&#x2022;Ě&#x201E; s | Îąj ) î&#x20AC;˛ln pm (aj)} Îąj î&#x20AC;ľ arg min{î&#x20AC;˛ln pv (Ď&#x2022;Ě&#x201E; s î&#x20AC;˛h(Îąj ) î&#x20AC;˛ln pm (aj)} Îąj

We use a priori information about polarization characteristics, the membership functions of which are shown in Fig. 7. After estimating these parameters, we calculate the potential distribution by a direct analysis using the estimated polarization characteristics.

The estimated potential distribution is shown in Fig. 8 and is found to agree well with the exact solution (Fig. 6).

Practical application.â&#x20AC;&#x201D;The inverse analysis method is applied for a real truss structure. The overview of the truss type structure is shown in Fig. 9. Over 90 pieces of aluminum anodes are attached to this structure. First, the actual potential distribution around the structure (continued on next page)

(16) (17)

Fig. 5. Location of electrodes and sensors.

The above approach is also termed â&#x20AC;&#x153;maximum a posterioriâ&#x20AC;?

(MAP) estimation. The mean value of the likelihood function can be the solution as well.

Verification Our primary aim is to verify the applicability of the inverse analysis in the estimation of the polarization characteristics. To concentrate on the evaluation of the process, we have created necessary measured data Ď&#x2022;Ě&#x201E; s through a regular/direct boundary element analysis instead of carrying out real potential measurements. Such a procedure allows the present technique to be isolated from other factors that can influence the accuracy and the convergence rate. However, to accommodate an important aspect of experimental measurements, a small perturbation/error is added to the calculated results. These values are assumed to be the measured potential value Ď&#x2022;Ě&#x201E; s and used in the inverse analysis to determine the polarization characteristics.

Direct analysis.â&#x20AC;&#x201D;Let us consider a ship that has six electrodes and six sensors as shown in Fig. 5. At first, we perform a direct analysis for the case where the current densities impressed to the electrodes on the left side of the hull are 0.04, 0.04, and 0.4 [A/m2] (from head to tail), and those on the right side of the hull are 0.01, 0.01, and 0.01 [A/m2] (from head to tail). We assume that that the hull is made of painted low alloy steel plates and their polarization characteristics are given by

î&#x20AC;˛1

Ď&#x2022; = î&#x20AC;˛0.600 sinh(200i) + 0.650

where the units of Ď&#x2022; and i are [V] and [A/m ], respectively.

The calculation is performed by employing 764 constant elements.

The estimated potential distribution is shown in Fig. 6.

The potentials at the location of the sensors are rounded off to three top figures to take into account the measurement accuracy, and are used as the input data in the following inverse analysis.

Estimation of potential distribution.â&#x20AC;&#x201D;In this inverse problem, we assume that only the potential data at the location of the sensors is available. At first, we estimate the polarization characteristics. We assume that the polarization characteristics of the painted hull are represented in the following form

î&#x20AC;˛1

Ď&#x2022; = î&#x20AC;˛Îą1 sinh(Îą2i) + Îą3

where Îąj(j = 1, 2, 3) is the parameter to be estimated.

The Electrochemical Society Interface â&#x20AC;˘ Winter 2014

1 0 -0.9

Îą1

-0.4

Îą2

500 [(A/m ) ]

Îą3

0.8 [V]

[V]

1

(18)

2

Fig. 6. Potential distribution obtained by a direct analysis.

(19)

0

0

1 0

0

Fig. 7. A-priori information of polarization characteristics as membership functions.

55

Amaya, Yoneya, and Onishi

Naoki Yoneya is a researcher at Hitachi, Ltd., in the Hitachi Research Laboratory Information and Control Systems Research Center, Green Mobility Research Department. His research interests are inverse problems and Bayesian estimation.

(continued from previous page)

is measured as shown in Fig. 9. Then, the relationship between the CP current and the potential distribution, which is represented by the observation equation, is quantitatively examined. A 3D finite element method is employed to simulate the potential distribution.

Finally, Bayesian estimation is performed to estimate the CP current.

The estimated potential distribution is shown in Fig. 10. It could be confirmed that the Bayesian estimation worked well for these kinds of corrosion engineering problems.

Yuki Onishi is an Assistant Professor in the Department of Mechanical and Environmental Informatics, Graduate School of Information Science and Engineering, at the Tokyo Institute of Technology. His research interests are Large Deformation FE/Meshfree Analysis, Vascular CFD Analysis based on 3D cine PC-MR (4D-Flow) Velocimetry, Cation Electrodeposition Simulation, and Multiphysics Localized Corrosion Simulation.

He may be contacted at yonishi@a.mei.titech.ac.jp.

About the Authors Kenji Amaya is the Professor in the Department of Mechanical and Environmental Informatics, Graduate School of Information Science and Engineering, at the Tokyo Institute of Technology.

Dr. Amaya’s research interests are in numerical simulation for corrosion engineering, electroplating, electrodeposition, and electropainting.

He is also interested in inverse problems including data assimilation. Dr. Amaya may be contacted at kamaya@mei.titech.ac.jp.

References 1. N. G. Zamani, J. F. Porter, and A. A. Mufti, A Survey of Computational Efforts in the Field of Corrosion Engineering, Int. J. Numer. Methods Eng., 23, 1295 (1986).

2. R. Strommen, W. Keim, J. Finnegan, and P. Mehdizadeh, Advances in Offshore Cathodic Protection Modeling using the Boundary Element Method, in Corrosion’86, p. 45, NACE, Houston, TX (1986).

3. R. A. Adey, C. A. Brebbia, and S. M. Niku, Application of Boundary Elements In Corrosion Engineering, in Topics in Boundary Element Research VII, C. A. Brebbia, Editor, p. 34, Springer-Verlag, Berlin, Germany (1990).

4. V. G. DeGiorgi, E. D. Thomas II, K. E. Lucas, and A. Kee, A Combined Design Methodology for Impressed Current Cathodic Protection System, in Proceedings of Boundary Element Technology XI, R. C. Ertekin, C. A. Brebbia, M. Tanaka, and R. Shaw, Editors, p.

335, Mechanics Publications, Southampton, England (1996).

Fig. 8. Estimated potential distribution.

džĂŵƉůĞ DĞĂƐƵƌĞŵĞŶƚ ĚĂƚĂ

ĞƉƚŚ ΀ŵ΁

WŽƚĞŶƚŝĂů΀s΁ DĞĂƐƵƌĞŵĞŶƚ ĂƚĂ

Fig. 9. Measured potential distribution around the truss structure in Tokyo Bay. 56

The Electrochemical Society Interface • Winter 2014

'HSWK>P@

3RWHQWLDO>9@

,GHQWLILHG 0HDVXUHG

Fig. 10. Identified potential distribution of whole surface of the truss structure in Tokyo Bay.

5. S. Aoki and K. Amaya, Optimization of Cathodic Protection System

by BEM, Eng. Anal. Boundary Elements, 19, 147 (1997).

6. S. Aoki and K. Amaya, Boundary Element Analysis of Inverse Problems in Corrosion Engineering, in Boundary Integral Formulations for Inverse Analysis, L. C. Wrobel and D. B. Ingham, Editors, p. 151, London, England (1997).

7. S. Aoki, K. Amaya, and M. Miyasaka, Boundary Element Analysis of Cathodic Protection for Complicated Structures, in Proceedings of Corrosion 99, M. E. Orazem, Editor, p. 45, NACE, Houston, TX (1999).

8. S. Aoki, K. Amaya, and M. Miyasaka, Analysis of Corrosion Problems by Boundary Element Method, in The Boundary Element Method, Vol. 1, p. 239, John Wiley, Tokyo, Japan (1998).

9. S. Aoki, K. Amaya, and H. Miyuki, Effective Boundary Element Method for Predicting Corrosion Rate of Heat Exchanger, in Proceedings of Computational Mechanics’95 Theory and Application, S. N. Atluri, G. Yagawa, and T. A. Cruse, Editors, p.

2714, Springer-Verlag, Berlin, Germany (1995).

10. K. Amaya, Development of Effective BEM for Galvanic Corrosion Analysis of a Slender Structure, Trans. JSME, 551, 1234 (1992).

11. K. Amaya, S. Aoki, H. Takazawa, M. Uragou, M. Miyasaka, An Efficient Boundary Element Method for Non-axisymmetric ThreeDimensional Corrosion Problems, in Trans. Appl. Mech., 177 (1999).

12. R. A. Adey, S. M. Niku, C. A. Brebbia, and J. Finnegan, Computer Aided Design of Cathodic Protection Systems, Paper presented at the International Conference on Boundary Element Methods in Engineering, Villa Olmo, Lake Como, Italy, September 24-27, 1985.

13. R. A. Adey and S. M. Niku, Computer Modelling of Corrosion using the Boundary Element Method, in Computer Modelling in Corrosion, p. 248, ASTM, Conshohocken, PA (1992).

14. G. Ozakan and Y. Mengi, On the Use of FFT Algorithm for the Circumferential Co-ordinate in Boundary Element Formulation of Axisymmetric Problems, Int. J. Numer. Methods Eng., 40, 2385 (1997).

15. K. Amaya, N. Naruse, S. Aoki, and M. Miyasaka, Efficient Boundary Element Method for Large Scale Corrosion Problems, Trans. JSME, 635, 1493 (1999).

The Electrochemical Society Interface • Winter 2014

16. A. Nakayama, M. Uragou, K. Amaya, and S. Aoki, Application of Fast Mulipole Boundary Element Method of Corrosion Problems, J. Soc. Mater. Sci. Jpn., 11, 1316 (1999).

17. K. Amaya, T. Kaneko, and S. Aoki, Effective Optimization of Cathodic Protection Design by Fast Multipole Boundary Element Method, Trans. JSME, 661, 1417 (2001).

18. M. G. Fontana and N. D. Greene, Corrosion Engineering, McGrawHill, Tokyo, Japan (1978).

19. C. A. Brebbia, The Boundary Element Method for Engineering, Pentech Press, London, England (1978).

20. J. Raamachandran, Boundary and Finite Elements: Theory and Problems, CRC Press, Boca Raton, FL (2000).

21. W. H. Press, Numerical Recipes in C: the Art of Scientific Computing, Cambridge University Press, Cambridge, England (1992).

22. M. Miyasaka, J. Ishiguro, K. Kishimoto, and S. Aoki, Application of BEM to Cathodic Protection of Seawater Pump, Paper 288 presented at Corrosion’95, Houston, TX (1995).

23. M. Tanaka and H. D. Bui, Editors, Inverse Problems in Engineering Mechanics, Springer-Verlag, Berlin, Germany (1993).

24. H. D. Bui, in Inverse Problems in Engineering Mechanics, (1994).

25. S. Aoki and Y. Urai, Inverse Analysis of Estimating Galvanic Corrosion Rate, in Inverse Problems in Engineering Mechanics, p.

547, Springer-Verlag, Berlin, Germany (1993).

26. K. Amaya, J. Togashi, and S. Aoki, Inverse Analysis of Galvanic Corrosion Using A Priori Information, JSME Int. J., 38-4, 541 (1995).

27. M. G. Fontana and N. D. Greene, Corrosion Engineering, McGrawHill, (1978).

28. C. A. Brebbia, The Boundary Element Method for Engineering, Pentech Press, London, England (1978).

29. S. Aoki, K. Amaya, and M. Hayase, Inverse Analysis for Improving Accuracy of SVET in Corrosion Study, in Inverse Problems in Engineering Mechanics, p. 176, Springer-Verlag, Berlin, Germany (1994).

57

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Modeling Corrosion, Atom by Atom

by Christopher D. Taylor

I

n the late 20th century, computer programs emerged that could solve the fundamental quantum mechanical equations that control the interactions of atoms that give rise to bonding. These tools, first applied to molecules and bulk solid materials, then began to be applied to surfaces and, in the early 21st century, to electrochemical environments.1 Commercial and open-source programs are now readily available and can be used on both desktop and highperformance computing platforms to solve for the electronic structure of a given configuration of atomic centers (nuclei) and, in so doing, provide the basis for determining a whole host of properties, including electronic and vibrational spectra, electrical moments such as the system dipole, and, most importantly, the energy and forces on the atoms.2-4 Other derived properties include the extent to which each atom is charged and bond-orders, although to compute these latter properties one of a variety of methods for dividing up and quantifying the electron density associated with each atom must be selected.5 The physics behind these codes is complex, and, challengingly, has no rigorous analytical solution that can be obtained within a finite allotment of time. Thus, the computer programs themselves take advantage of approximations that allow for a feasible solution but, at the same time, constrain the accuracy of the result. Nonetheless, solutions can usually be reliably obtained for model systems representing materials, interfaces, or molecules that do not exceed thousands, and, more realistically, hundreds of atoms.6 Given that system sizes of hundreds or thousands of atoms amount to no more than the smallest nanoparticle of a substance, the question arises: What can atomistic simulations teach us about corrosion?

The answer to this question lies in the ability for atomistic simulation to confirm or deny key hypotheses associated with potential corrosion mechanisms. By directly simulating the structure of a molecule, its spectroscopic signatures, or the energetics of the bond-making and bond-breaking processes it engages in, much information can be gained that is useful to the interpretation of

experiment and the verification of proposed theories. For instance, if a certain mechanistic step has a considerably large activation barrier (as computed from quantum mechanics), we can assume that it will not proceed unless somehow catalyzed. Furthermore, if a given atomic configuration is found to be metastable through molecular simulation, then we can predict that, over time, it will decay to a lower energy state. Furthermore, using periodic boundary conditions, it is possible to mimic the effects of semi-infinite surfaces (thus effectively going beyond the hundreds or thousands of atoms limit), albeit ensuring that careful attention is paid to address spurious results that may arise from image-image interactions.

In this report we give several examples. In the first case we show how the computation of the properties of molecular systems can provide some insight as to their overall properties, and draw an example from the field of molecular design of corrosion inhibitors.

In the second, we show how periodic boundary conditions can be applied to simulate the chemisorption of environmental species, such as chloride, hydroxide and ammonia, on to semi-infinite metallic surfaces. Then, we show how this technique can also be applied to simulate the structure and properties of the metal/oxide interface.

Finally, we provide an illustration of how atomistic methods are being used to begin to simulate the challenging topic of modeling the non-equilibrium states associated with material dissolution.

Designing Corrosion Inhibitors Quantum chemical evaluation of corrosion inhibitors began with Vosta and Eliasek in 1971.7 Since then, the ability to rapidly evaluate the molecular structure and electronic properties of relatively small inhibitor molecules (dozens of atoms) has led to a proliferation of similar studies, at varying levels of sophistication (Fig. 1). At one (continued on next page)

Fig. 1. Two approaches that utilize quantum mechanics to model inhibitor performance. Reproduced with permission from Ind. Eng. Chem. Res. 52 1487514889 (2013) (Š American Chemical Society, 2013) and J. Am. Chem. Soc. 132 16657-16668 (2010) (Š American Chemical Society, 2010).

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Competitive Adsorption and Ammonium Chloride Corrosion

(continued from previous page)

extreme, data-driven approaches take the outputs of quantum chemical simulations (atomic charges, electronegativity, the energy gap between filled and unfilled molecular orbitals) as descriptors that are correlated against inhibitor efficiency with machine-learning approaches. This approach is called QSAR: quantitative structure active relationships.8-15 At the other extreme, direct simulation of the inhibitor binding mode to a metal surface has been used to address the fundamental mechanisms of inhibition.16-23 The relationship of inhibitor efficiency to the quantum mechanical properties of the inhibitor molecule is quite complex. Inhibitor molecules typically have a three-part structure, consisting of an anchor chemical group (like an amine, thiol, or imidazoline group), a backbone (for example, a saturated or unsaturated carbon chain), and substituent groups that have been suggested to provide fine-tuning of the surface-inhibitor interaction and the inhibitor-inhibitor interactions that control the properties of the self-assembled monolayer that forms upon inhibitor adsorption.24,25 The interaction of the inhibitor with the material itself will depend upon the composition, crystal structure, and uniformity of the outermost layers of the material, possibly sulfides, oxides or oxy-hydroxides, or, where the passive layers have been breached, a bare metal surface itself. Molecular simulation makes it possible to begin to deconstruct the various elements of this problem, and, as each element becomes tractable with time, they can then be reconciled to form an overall multiscale model.

The QSAR approach implicitly combines all of these complex micro-processes together and proposes that the inhibitor efficiency, like any physical observable, A, should be obtainable (at least in principle) by applying the appropriate quantum mechanical operator, , to the wavefunction Ψ via the inner-product3

+

*

〈A〉  Ψ Ψ dx =〈Ψ Ψ〉

(1)

The challenge to the QSAR community is that the quantum mechanical operator for inhibitor efficiency is not well known, and must be dependent upon several factors, such as surface quality, pH, temperature, ion-speciation, etc. The premise behind the QSAR approach, then, is that given the mystery surrounding the proper mathematical form of the operator , it might instead be possible to approximate in terms of the other, more readily computable, molecular properties. Hence the use of machine-learning approaches to parameterize the inhibitor efficiency in terms of a growing set of molecular descriptors that may or may not have any direct relevance to the inhibitor mechanism. The key dangers in this approach are over-fitting of the black-box numerical model due to the relative abundance of quantum chemical descriptors compared to the relatively small set of inhibitor efficiency data points, and the likely possibility that the quantum chemical descriptors alone may not be sufficiently informative for capturing the complexity of the moleculesurface interaction.

The mechanistic approach, on the other hand, is more timeconsuming, and requires a significant investment of research labor and cpu-hours to deconstruct the inhibition mechanism across the environment, interfacial, and near-surface domains into its elements and then reassemble them into a comprehensive science-based model. Pieces of this model, attainable through current molecular simulation methods, include the calculation of partition coefficients of the inhibitor between oil (or polymer) and aqueous phases,26 the effect of the inhibitor molecule on multiphase flow,27 the simulation of inhibitor diffusivity and the calculation of pKa’s,28 the adsorption of the inhibitor molecule onto various possible surface phases and presentations (i.e., exposed Miller indices),19,20,22,29-36 and the efficiency with which the inhibitor molecules can form a coherent, self-assembled monolayer that adequately protects the surface from corrosion.24,37,28 Given that these kinds of simulations are more configurationally complex, progress in this area is on-going; more time consuming than the QSAR methods, but with potentially higher pay-offs in terms of understanding and inhibitor design.

60

Ammonium chloride salts that form due to the combination of ammonia and hydrogen chloride vapors during industrial refining can lead to severe corrosion when they absorb water from the atmosphere, forming highly saturated salt solutions containing ammonia, ammonium cations, and chloride anions as well as water and its dissociation products H+ and OH−.39-43 To address some mechanistic aspects of the corrosion system that forms due to the uptake of water by ammonium chloride salts (i.e., a phenomenon known as deliquescence), we used density functional theory to calculate the free energy change associated with the adsorption of these ions from the aqueous phase to an iron surface (used to mimic the surface of the mild steel; it was assumed that, in the worst case, depassivation had already occurred).44 For example, the adsorption of chloride leads to a free energy change associated with the reaction

Cl−(aq) + *  Cl(ads) + e−

(2)

where * indicates a vacant adsorption site on the metal surface (possibly occupied by water, or one of the other ions present, Fig 2).

On the other hand, it is possible that water can adsorb, with the loss of a proton to form a surface adsorbed hydroxide, via the reaction

H2O(aq)  OH(ads) + H+ + e−

(3)

The free energy consists of the internal energies of the atoms and molecules, that are defined by their electronic and nuclear structure, the enthalpies and entropies associated with the vibrational modes (these are determined by quantum mechanics), configurational entropy (which is dependent upon the concentration in solution, and the acid-base equilibria), and the pH and electrochemical potential.45 By calculating the free energy of chemisorption from a combination of the calculated surface adsorption energies, tabulated data for pKa’s and the chlorine/chloride electrochemical potential, it was possible to then rank the ions according to their tendency to adsorb on the metal surface. Consequently, it was discovered that there exist particular regions of pH and potential in which the chloride ion has sufficient thermodynamic driving force to interfere with the adsorption of oxygen, thus limiting the surface’s ability to protect itself through repassivation. The pH-potential regimes identified correlate with the boundary conditions observed in the field for ammonium chloride corrosion.41,42,46 In this way, atomistic simulation was used to provide an explanation for the role of ammonium chloride salts in accelerating corrosion of mild steel.

Understanding Passivity

by Modeling Metal/Metal-Oxide Interfaces It has been remarked that the self-limiting formation of oxide films is a vital condition for the metals-based civilization that humanity presently enjoys.47 While oxides and metals are both relatively well understood from a crystallographic point of view, the structure of the thin films of oxides that passivate metal surfaces is not as well defined, and may vary depending on the crystallographic orientation of the surface, the electrochemical or atmospheric growth conditions, and the presence of impurities and other anion/cations that may be present in the environment. Furthermore, the interface provides an unusual two-phase state, whereby the symmetries, bonding and charge-states of the metallic and oxide phases must achieve a compromise that optimizes the Gibbs’ free energy within the given kinetic constraints. Atomistic simulations provide a means for sampling this potential energy surface as a function of the possible geometric arrangements of ions and neutral species that might exist at the metal/oxide interface.

The transition from chemisorbed layers to the first few layers of oxide on nickel was examined for close-packed and stepped surfaces using density functional theory.48 The gradual evolution of the Ni2+ The Electrochemical Society Interface • Winter 2014

charge state was monitored as a function of the extent of this initial oxidation. Differential activities were also observed for step sites compared to the terraces. The oxidation of nickel was observed to proceed first by a gradual filling of the first monolayer of the surface with oxygen, and then by a reconstructed layer that created a mixed Ni-O-Ni bilayer. A key mathematical physics challenge still needs to be resolved for accurately simulating such two-phase systems, due to the very different electron correlation properties of the oxide phase versus the metallic phase. Similar studies have been performed on Tc(0001) (see Fig. 3), Mg(0001) and Pt(111).49-51 Molecular dynamics simulations based upon the use of classical interatomic potentials have been performed for studying the passivation of metals including nickel, iron, aluminum, and zirconium.52-54 The development of “reactive force fields” has allowed a new generation of molecular dynamics simulations to be performed that can take into account not only changes in local geometry of atoms, but also changes in their oxidation state, which typically lead to more drastic changes in the properties of the material.55,56 These simulations have been used to examine the mechanisms of oxide growth (as mediated by point-defects), and the effects of temperature and surface orientation.

Watching Virtual Metal Atoms Dissolve The process of metal dissolution involves some mystery, due to the transition of a neutral metal atom bound to its neighbors through metallic bonding across the electrochemical double layer, and its emergence as a cationic species with its own solvation shell and shed of its excess valence electrons. The unresolved physical issues surrounding this phenomenon have in recent years been highlighted in a series of papers by Eliezer Gileadi.57-59 Considering the quantum and atomistic nature of this process, it is well suited to investigation by quantum chemical simulations. However, there are a number of hidden complexities to the problem. An effort combining molecular dynamics and constrained geometry optimization was made to simulate the process by which Cu adatoms dissolve from a

nanoparticle surface facet.60,61 The change in potential energy of the dissolving ion, as a function of its progress across the electrochemical double layer was shown to be highly dependent on the extent to which the coordination sphere of water molecules was allowed to relax.

This last point was found to be potentially the greatest limitation to contemporary simulations of the dissolution process.

A multiphysics approach was made by Pinto et al. who used the electron transfer theory of Marcus-Hush to model the deposition of a silver atom in its neutral/cation superposition state as it crossed the electrochemical double layer.62-64 Using classical molecular dynamics the authors showed that the silver cation could in fact retain a large portion of its solvation sheath quite close to the electrode.

Quantum mechanical evaluation of the density of states was used to estimate the coupling constant for electron transfer and the attachment energy of silver atoms from the terrace to the kink sites on the surface. Collectively, the results showed that silver ions have a rapid deposition (and, therefore, dissolution) rate due to the ability for the solvated ion to approach very close to the electrode surface, and the long-range overlap of the silver ion’s s-orbital with the spband of the electrode. For multivalent ions, it was suggested that a series of one-electron steps would be required, as the multivalent ions possess strong secondary solvation sheaths that would prevent as close an approach to the electrode as permitted to the univalent silver. Although the focus of the paper was on deposition, the same logic applies to the process of dissolution.

Summary Remarks Atomistic models based upon the fundamental quantum mechanical interactions between ions and electrons are currently being used to assess the quality of proposed mechanisms in corrosion science, as well as providing quantitative insights into the thermodynamic and kinetic constraints associated with these mechanisms. Currently, the limitations of the methods restrict modeling to systems of “molecular” proportions, or, when using periodic boundary conditions, to relatively idealized (i.e., high translational symmetry) two-dimensional systems (continued on next page)

Cl

NH3

Fig. 2. Ball and stick representation of the optimized geometries of (a) chloride and (b) ammonia on the Fe(110) surface.

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(continued from previous page)

such as low-index surfaces. Three-dimensional periodic models have been used to model the interaction of impurity elements, such as hydrogen, with point-defects.65 To conclude this overview, three categories of atomistic modeling for corrosion science are suggested: • Available now: Calculation of molecular and surfaces properties for comparison with experiment, such as vibrational mode analysis and bond-lengths; prediction of thermodynamic properties of stable and metastable phases, such as twodimensional surface phases; assessment of kinetic barriers to non-electrochemical reactions; limited treatment of the role of electrode potential and solvent in affecting reaction kinetics.

• Challenging but possible to achieve with current methods: Simulation of metal/metal-oxide/oxy-hydroxide interfaces through classical and charge-transfer interatomic potentials; properties of inhomogeneous alloy systems; treatment of dynamic complexity in solvent rearrangement by the metal/ electrolyte interface; the role of point- and line-defects in corrosion mechanisms.

• Longer standing challenges requiring algorithmic and computational advances: Multiphysics and multiscale integration of quantum mechanics and classical molecular dynamics simulations with coarse-grained and continuum level models, including at the process engineering scale; accurate treatment of electron transfer and solvent rearrangement effects on the kinetics of electrochemical reactions; quantification of uncertainty from fundamental physics-based models and its propagation across multiscale hierarchies.

About the Author Christopher D. Taylor is a Senior Research Scientist at DNV GL’s Materials Research and Innovation division located in Dublin, Ohio. Dr. Taylor also holds a position as Associate Research Professor in the Fontana Corrosion Center in the Materials Science and Engineering Department at The Ohio State University. Dr. Taylor’s research focuses on linking fundamental atomistic and molecular simulations of the microprocesses responsible for corrosion within the context of multiscale/multiphysics models for the purposes of lifetime prediction, materials design, and risk assessment. Dr. Taylor received his BSc with Honors in Chemistry at the University of Western Australia, and his MS in Chemistry from the University of Memphis.

He received his PhD in Engineering Physics from the University of Virginia under the direction of Robert Kelly (Materials Science & Engineering) and Matthew Neurock (Chemical Engineering). He may be reached at Christopher.Taylor@dnvgl.com.

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electrochem.org The Electrochemical Society Interface • Winter 2014

Computer Simulation of Pitting Corrosion of Stainless Steels

by N. J. Laycock, D. P. Krouse, S. C. Hendy, and D. E. Williams

S

tainless steels and other corrosion resistant alloys are generally protected from the environment by ultra-thin layers of surface oxides, also called passive films. Unfortunately, these films are not perfect and their Achilles’ heel is a propensity to catastrophic local breakdown, which leads to rapid corrosion of the metallic substructure (see Fig. 1). Aside from the safety and environmental hazards associated with these events, the economic impact is enormous.1 In the oil and gas and petrochemical industries, it is of course usually possible to select from experience a corrosion-resistant alloy that will perform acceptably in a given service environment.

This knowledge is to a large extent captured in industry or companyspecific standards, such as Norsok M1.2 However, these selections are typically very conservative because the limits tend to be driven by particular incidents or test results, rather than by fundamental understanding. Decision-making can be very challenging, especially in today’s mega-facilities, where the cost of production downtime is often staggeringly large. Thus significant practical benefits could be gained from reliable quantitative models for pitting corrosion of stainless steels. There have been several attempts to develop purely stochastic models of pitting corrosion.3-6 On the other hand, purely deterministic models7,8 have also been proposed.

The critical processes involved in pitting corrosion can be clearly separated into those involved in initiation, nucleation of a ‘metastable’ pit, and propagation or maintenance of the stability of growth of the initially formed defect.9 Fluctuations in current signal the nucleation, temporary growth, and cessation of growth (‘death’) of metastable pits. A steadily increasing current signals the formation of a pit whose propagation continues. Analysis of these current fluctuations leads to a simple idea connecting the frequency of initiation of metastable pits, λ, with the frequency of formation of stable pits, Λ

Λ = λ exp(−µtc)

(1)

where µ denotes the probability of ‘death’ of a metastable pit and tc is a ‘critical age’: if the metastable pit continues to propagate for a time longer than tc, then it transitions to ‘stability’.9 Within a pit of any size, the solution conditions are extreme and very different from those outside the pit (Fig. 2). The questions for modeling are therefore (a) for initiation, how are the required extreme

gradients developed in the first place, and (b) for propagation, how are they maintained. Development of a reliable predictive model for pitting corrosion in industrial service conditions requires a robust model for both the pit nucleation and pit propagation processes.

Moreover, fundamental improvements in the performance of the less-expensive stainless steels are at least as likely to come from manipulation of the nucleation process as from further effects on pit propagation.

Pit Nucleation: Passive Film Formation and Breakdown The nucleation stage of pitting corrosion involves the breakdown of the protective passivating layer; the establishment of the extreme local gradients that drive propagation and its mechanism is the subject of intense debate.10-15 Metastable pit nucleation in commercial alloys is dominated by processes at sulfide inclusions.17 This region adjacent to MnS inclusions has been shown to be an area of high electrochemical activity.10,18 An unusually high-rate dissolution of MnS inclusions has been shown to lead to a sulfur crust over the inclusion, and it is assumed that the steel passivity then breaks down within the aggressive solution formed underneath this crust as a consequence of dissolution of the inclusion.19 An Fe(Mn)S layer around the inclusion rim, detected by high-resolution SIMS microscopy, has been proposed as the cause of the initial inclusion dissolution.16 These observations point to passive film breakdown in a sulfide-chloride solution formed by inclusion dissolution as the critical event. Similarly, the deleterious effect of the sigma phase in duplex stainless steels may also be caused by a locally Cr-depleted zone that is more susceptible to pitting than is the surrounding matrix. Pits will also nucleate on inclusion-free materials20 and tiny current fluctuations that are assumed to represent possible trigger events (and are not associated with inclusions) have been detected in electrochemical imaging experiments.21 For the Fe-Cr alloy system, various experimental results have been interpreted using a passivation model proposed by Sieradzki and Newman,22-25 which provides a framework for understanding compositional thresholds for passivity and the effect of variations (continued on next page)

(a)

(b)

Fig. 1. (a) Extensive pitting corrosion damage beneath thick deposits on a SAF2205 duplex stainless steel heat exchanger tube with cooling water on the shell side; (b) pitting corrosion in 316 SS heat exchanger tubes unintentionally exposed to high chloride brine in a geothermal power station.

The Electrochemical Society Interface • Winter 2014

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Laycock, et al.

(continued from previous page)

of Cr content on susceptibility to pitting corrosion. The model is based on the application of percolation theory, which quantifies the connectivity of a “random medium.” In this model, the passivation of Fe-Cr alloys in acid solutions is due to formation of solid Cr (hydr)oxide with concurrent selective dissolution of Fe. Further Fe dissolution is eventually blocked by stable (-O-CrOH) chains, the formation of which depends critically on the connectivity of Cr atoms within the alloy lattice. We have carried out simulations of passivation for Fe-Cr (bcc) alloys in ideal situations, and the results are consistent with a variety of experimental results.26 These ideas have led to a proposal for passive film breakdown that has been explored by computer simulation.12 Nanoscopic clusters that contain only iron atoms would be randomly distributed throughout the material, therefore occasionally becoming exposed to the electrolyte simply through the slow dissolution of the passive film, and would then rapidly dissolve, to create a nanoscopic cavity with relatively Cr-rich boundaries. The speculation is that the resultant current pulse might create a local environment that might cause further dissolution of the boundaries of the cavity. In this model, the probability of the existence of a critical cluster size is the key factor in determining the likelihood of pitting, and it can be related to the alloy content via a percolation type model. For the binary Fe-Cr (bcc) lattice Pc(1) is 0.25. Hence there are “infinite” chains of Fe atoms in 1st nearest neighbor sites for Fe contents above 25%. However, if we define an Fe cluster as a chain of Fe atoms that have only Fe atoms as 1st nearest neighbors, then Monte Carlo simulations show that these clusters have a Pc of approximately 0.85. Simulations were performed with a bcc lattice containing 3,953,501 atoms arranged in a cube, with lattice points randomly assigned as Fe or Cr atoms in the desired proportions. In each of 1000 simulations, Fe clusters anchored at the top surface were counted for size and depth. Figure 3 shows an example of a large (but not “infinite”) cluster. Initial results suggest a surface number density of potential nucleation sites of about 10 to 100 cm−2. This remains 3-4 orders of magnitude lower than the total number of events observed in our experiments with high-purity metal films.27

Propagation Pit nucleation events occur at a very high frequency, even in conditions where stable pits do not form.10,17,28 The transition from nucleation event to propagating pit depends on the fact that, in chloride solutions, the solution within the incipient pit cavity becomes highly acidic and concentrated in chloride, thus permitting the metal

to dissolve actively instead of passivating. The concentration of dissolved metal cations (Fe and Cr) at the metal surface controls the local pH via the following hydrolysis reaction:

M z+ + y H2O → [M (OH)y](z-y)+ + y H+

(2)

where M represents a metal cation and z can be 1, 2, or 3, with a decreasing equilibrium pH and a decreasing rate of reaction as z increases. Chloride ions also migrate into the corrosion site to balance any excess of metal cations, and there is an additional acidification because the highly concentrated chloride solution has a mean ionic activity coefficient greater than one. At the same time, there are concentration and potential gradients that lead to transport of metal ions out of the pit. Thus, a pit will only initiate (i.e., continue to propagate after a nucleation event) if the metal can dissolve fast enough to maintain the local environment that will sustain this dissolution. The critical solution chemistry for 300 series stainless steels at ambient temperature is about 70% of saturation in metal chloride. This approach derives essentially from the work of J. R. Galvele,29,30 as described in detail in an earlier edition of Interface.31 We believe that almost all the alloying and environment effects in localized corrosion of stainless steel can be explained using this basic idea.

A model along these lines for propagation of single pits has been presented in detail elsewhere.32-35 The local chemistry is modeled using the method proposed by Sharland,36 and then anodic and cathodic reactions in the concentrated pit solutions are modeled on a semi-empirical basis, with parameters for a particular set of conditions determined by comparing the predictions of the model against experimental results from various artificial pit experiments.

For metal inside a propagating pit, we assume that anodic dissolution obeys Tafel’s Law such that at an applied potential of Eapp, the anodic current density, ia, at any point on the pit surface is given by

 i Eapp = Ecorr + ba log a  icorr

  + φs + φϕsfsf 

(3)

where ia is the anodic current density, ba is the anodic Tafel slope, Ecorr and icorr are the open-circuit corrosion potential and corrosion current density (within the local pit environment), ϕs is the ohmic potential drop in solution, and ϕsf is the potential drop across any precipitated salt film on the corroding surface. This equation gives the anodic current density at any surface point within the pit, provided that the solution at that point remains concentrated enough to prevent passivation, and the repassivation process is modeled using the method described in Ref. 35.

In the early work, we assumed that each pit is initially a hollow truncated sphere with an open “mouth” at a perfectly flat metal surface. Later, we introduced surface roughness, as described in Ref. 37. The key results of such simulations are as follows. For a given initiation site, the lifetime of the pit depends on potential. At low potentials, pits cannot be initiated in this particular cavity and the lifetime is effectively zero. Above the first critical potential, Em, pits can be initiated, but they have only a finite lifetime before spontaneously repassivating.

This behavior, known as metastable pitting, is shown by the anodic current transient at the lower applied potential in Fig. 4. Above a second critical potential, Es, the pits do not repassivate within the time scale of our simulations (also shown in Fig. 4) and are assumed able to propagate indefinitely; i.e., they are considered to be stable pits.

The values of Em and Es also depend on the initiation site geometry, as discussed in detail elsewhere.35,37

Fig. 2. Comparison of conditions inside and outside a pit, illustrating the extreme gradients that are established.

66

The Electrochemical Society Interface • Winter 2014

Combining Nucleation and Propagation Models A pragmatic model with predictive capability can be constructed by combining the deterministic model for the propagation of single pits in stainless steel with a stochastic model of pit nucleation. The deterministic model replaces the empirical ‘pit death’ probability, µ, and ‘critical age’, tc, in Eq. 1.

There is assumed to be a fixed initial density of possible nucleation sites and if a pit nucleates at a site (frequency λ), then that site is removed from the simulation. The model can be used to simulate potentiostatic or potentiodynamic experiments using samples on which there are many possible pitting sites, and the results of model simulations show very good quantitative agreement with experimental results for the effects on the pitting potential of molybdenum alloying, surface roughness and potential scan rate,37 temperature,34 and solution chloride concentration.38

Multiple Pit Interactions For a stainless steel to be immune from pitting corrosion in a chloride-containing service environment, the maximum opencircuit potential of the passive steel must be lower than its ‘pitting potential’ in that environment. This understanding has been gained in large part through laboratory measurements of the ‘pitting potential’, and most of these experiments have been performed using potential-control of small samples.

Research in this area has generally focused on the critical factors determining the growth stability of individual pits,39-42 although more recently there has been increasing interest on the interactions between pits.43-45 However, real corrosion does not occur under potentiostatic conditions; rather, there is a limited supply of cathodic current that must be shared between all simultaneously propagating pits. This situation is somewhat more closely resembled by experiments under galvanostatic control.46,47 A multiple-pit version of the singlepit algorithm has been implemented using the standard parallel processing library, MPI. Propagation of each pit is assigned to a separate process and these processes communicate the information required to update the effective bulk concentration and applied potential at each time step. The pit initiation process at any given initiation site is deemed to create a saturated local chemistry within that pit cavity, and all the applied anodic current must be used by propagating pits. Thus, if only one pit is initiated at the start of a simulation, the first few iterations of the simulation will determine an Ea value that supports propagation of that pit at the selected applied current. If the applied current is too low, no solutions will be found and the simulation will end. (continued on next page)

The Electrochemical Society Interface • Winter 2014

z

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y

x

Fig. 3. Large Fe-cluster in a Fe-Cr 16% alloy. The cube shows the boundary of a bcc lattice of 3,953,501 atoms. Only the Fe atoms within the large cluster are shown in black.

Fig. 4. Model current transients from a single simulated pit in 316 stainless steel, propagated at 170 mV or 190 mV in 1 M NaCl.35

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(continued from previous page)

68

15 10 5 0 0.0

0.5

1.0

1.5

2.0

2.5

3.0

Time (s)

5

10

15

Galvanostatic

0

In the atmospheric corrosion of stainless steel, airborne salts are deposited on exposed metal surfaces with a certain deposition density (DD, g/ cm2). Then, depending on the specific composition of the deposited salts and atmospheric relative humidity (RH), the salts absorb moisture from the air to create a thin liquid layer with the equilibrium concentration of dissolved salt. For deposited MgCl2 salts, Tsutsumi et al.,49 found that pitting corrosion of 304 stainless steel under these conditions initiated when the RH was ~ 65%, corresponding to a dissolved chloride concentration of ~ 6M. To simulate long-term atmospheric exposure of stainless steel, we have coupled the pit propagation model adapted to high chloride conditions38 with a cathode model similar to that developed by Chen et al.50,51 Our main difficulty has been in extending the time scales of computer simulations from tens of seconds to the much longer times necessary to assess whether a pit has indeed reached a maximum size. We have been able to overcome some of these problems using a method of ‘quasi-steady state’ simulation in which the pit grows at the current required to maintain a chloride dependent critical concentration of metal ions on the bare metal surface. The results of simulations employing this model indicate that a pit growing under a thin liquid film adapts to the cathodic current limitation by adopting a shallow dish-shaped morphology, in which the current becomes confined to a decreasing lateral area of the pit as the bottom of the pit repassivates, while the lateral surfaces are able to grow. Using relatively aggressive conditions of continuous high DD and high RH to simulate a worst case scenario, the model predicts a maximum depth of pits of the order of 100–300 microns attained over periods of several months, as shown in Fig. 6.52 Both the time scales and depths predicted by the model are consistent with available field data, although such data are insufficiently time resolved to be able to attempt a rigorous validation of the model. In particular, quantitative data on long-term pit growth for stainless steel under atmospheric conditions show a relatively limited variability in maximum pit depths under similar exposure conditions.

Number propagating

Long-Term Predictions

Potentiostatic

Number propagating

In this model, there are two ways in which a propagating pit will influence a nearby pit; via a local increase in the chloride concentration, and via changes in the local effective applied potential.

Simulations for regular arrays of identical pit initiation sites (Fig. 5) show a negative impact of pit interactions in galvanostatic conditions, with pits having the greatest number of neighboring pits being the first to repassivate. This is due to the depression of the effective applied potential around each propagating pit. Introducing variations in the spatial distribution, geometry and initiation time for each pit results in increasingly complex behavior due to the unique conditions experienced by each pit during the period of the simulation.48

0

2

4

6

8

10

Time (s)

Fig. 5. Multiple pit simulations in 1M NaCl.48 16 pits with random initial radii between 10 and 40 microns were initiated at random starting times (between 0 and 1s) with one pit started at time zero. Galvanostatic and potentiostatic runs for comparable initial conditions: Eapp = 0.1 V, Iapp = 30 µA. The Electrochemical Society Interface • Winter 2014

The Future A full description of the pitting corrosion of stainless steels will require a multiscale modeling approach that combines fully three-dimensional simulations of the propagation of multiple pits with electrochemically accurate pit nucleation models. The influence of external pits on the propagation of a single pit is currently only treated in two-dimensions, with simulations of individual pits restricted to cylindrical symmetry, and the physical overlap of pits is ignored.

Moving to three-dimensions may well alter the type of behavior seen in two-dimensional multi-pit simulations, but such simulations will be highly computational intensive. Hence, the first steps toward simulations of threedimensional pit propagation will likely need to treat multi-pit interactions using a mean-field or homogenization approach.53 Pit nucleation models need to be based on a quantitative understanding of both the kinetics of oxide formation and dissolution54 and the thermodynamic stability of the nanocrystalline passive film.55,56 First principles calculations have been used to investigate the thermodynamic stability of the iron-chromium oxides that passivate Fe-Cr alloys in acidic environments.53 In situ X-ray diffraction suggested that these oxide films have a nanocrystalline spinel structure with a stoichiometry of the form Fig. 6. Model results for the depth of a single propagating pit in 304 SS growing under atmospheric Fe3â&#x2C6;&#x2019;2xCr2xO4.56,57 These films are observed to be conditions with varying chloride deposition density (DD) and relative humidity (RH). The fluctuations in calculated depth arise from the errors in the finite element approximation used to implement the enriched in Cr, compared to the bulk Fe-Cr alloys model.52 that they passivate, and density functional theory calculations suggest that the observed principles calculations, can access much larger time and spatial scales Cr enrichment in the films55 are in fact a necessary requirement for than molecular dynamics methods, while allowing for a degree of passivity. This is consistent with the Sieradzki-Newman model of chemical accuracy (especially compared to the heuristic approach the passivation of Fe-Cr alloys described above,22,23 where selective of the percolation simulations described above). In principle, dissolution of Fe would result in a Cr-rich surface layer that oxidizes KMC methods can be coupled to continuum simulations,64 which to form a thermodynamically stable Cr-enriched oxide. This also has would enable a dynamic treatment of the external electrochemical implications for our understanding of the breakdown of passivity, as environment, and could handle complex interfacial reactions.65 the local depletion of Cr in the oxide would lower the thermodynamic stability of the film in the acidic microenvironments that become established at incipient localized corrosion sites.58 Acknowledgments While such thermodynamic considerations are suggestive, the kinetic stability of these films is much more difficult to model This work was primarily supported by the NZ Ministry for on an atomistic scale. As a result many models of film kinetics Business Innovation and Employment under various contracts, and treat the passivating oxide layer as homogeneous,59 despite its by the UK Nuclear Decommissioning Authority under contract NR evident nanocrystalline structure and the fact that first principles 3274. calculations of ion transport through the passive layer54 suggest that About the Authors the nanocrystalline grain boundaries provide the dominant pathway for the passive current. This in turn suggests that the grain boundary Nicholas J. Laycock is currently a Senior structure, which itself will evolve over time, may play an important Materials & Corrosion Engineer for Shell at the role in the evolution of local Cr content in the alloy. Indeed, first Pearl GTL facilities in Qatar, and an Honorary principles methods have also been used to study the role of extended Senior Research Fellow in the School of surface defects, such as step edges, on film stability60,61 and it should Metallurgy and Materials at the University of eventually be possible to extend these to grain boundaries.

Birmingham. He joined Shell in New Zealand in Bridging the gap between our understanding of the nanoscale 2006 and before that he was a researcher and structure of passive films and the phenomenological models of consultant, specializing in localized corrosion. pit initiation will also require a multiscale modeling approach.62 He has authored about 90 peer-reviewed papers Increases in computational power, new techniques for accelerating and is an Associate Editor of Corrosion Science atomistic simulation methods, and effective approaches to coupling journal.

Nick has an MSc and PhD from the Corrosion & Protection these atomistic techniques to continuum methods will be needed Centre at UMIST, and has received the Shreir Award (1994) and Hoar to resolve the nanoscale heterogeneity of passive films, and Award (1997) from ICorr, and the Guy Bengough Award (2013) from capture processes with timescales as widely separated as metal ion the Institute of Materials, Minerals & Mining. He may be reached at dissolution and structural relaxation. Kinetic Monte Carlo (KMC) Nick.laycock@shell.com.

63 methods, with transition rates parameterized by the results of first (continued on next page)

The Electrochemical Society Interface â&#x20AC;˘ Winter 2014

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(continued from previous page)

Donal P. Krouse is a Senior Research Scientist at Callaghan Innovation, which is a New Zealand Crown entity. He has worked as a government scientist and consultant since 1986, specializing in mathematics, statistics and computational modelling. Donal has a BSc(Hons) in pure mathematics from the University of Otago and a post-graduate diploma in statistics and operations research from Victoria University. His work in corrosion focuses on pitting corrosion and includes the development of both stochastic and deterministic damage prediction models. He jointly received the Guy Bengough Award (2013) from the Institute of Materials, Minerals & Mining for a paper on pitting corrosion of stainless steel. He may be reached at Donal.

Krouse@callaghaninnovation.govt.nz.

Shaun C. Hendy is Director of the Te Pūnaha Matatini, a Centre of Research Excellence for Complex Systems and Networks, and a Professor of Physics at the University of Auckland. Shaun has a PhD in physics from the University of Alberta in Canada and a BSc(Hons) in mathematical physics from Massey University.

He has a wide range of research interests, including computational physics, nanoscience, complex systems and innovation. In 2010, Shaun was awarded the New Zealand Association of Scientists Research Medal and a Massey University Distinguished Young Alumni Award.

In 2012 he was elected a Fellow of the Royal Society of New Zealand for his research on nanotechnology, and in 2013 he was awarded ANZIAM’s E. O. Tuck medal for research in applied mathematics.

Shaun blogs, writes for Unlimited Magazine and has a regular slot on Radio New Zealand Nights as physics correspondent. In 2012, Shaun was awarded the Callaghan Medal by the Royal Society of New Zealand and the Prime Minister’s Science Media Communication Prize for his achievements as a science communicator. His first book, Get Off the Grass, co-authored with the late Sir Paul Callaghan, was published in August 2013. He may be reached at shaun.hendy@ auckland.ac.nz.

David E. Williams is a graduate of the University of Auckland. He developed his research career in electrochemistry and chemical sensors at the UK Atomic Energy Research Establishment, Harwell, in the 1980s. He became the Thomas Graham Professor of Chemistry at University College London in 1991 and co-founded Capteur Sensors Ltd. He was Head of the Chemistry Dept at UCL from 1999-2002 and co-founded Aeroqual Ltd .

He was Chief Scientist of Inverness Medical Innovations, based at Unipath Ltd, Bedford, UK, from 2002-2005.

He joined the faculty of the Chemistry Dept at Auckland University in February 2006. He is a Principal Investigator in the MacDiarmid Institute for Advanced Materials and Nanotechnology. He is an adjunct Professor at Dublin City University where he was Principal Investigator of the Biomedical Diagnostics Institute and Walton Visiting Fellow of Science Foundation Ireland. He is also a Visiting Professor at University College London and University of Southampton, and has been Honorary Professor of the Royal Institution of Great Britain, Visiting Professor at University of Toronto and at Cranfield University of Technology. He has published over 200 papers in international journals – on electrochemistry, surface science of biomedical devices, semiconducting oxides as gas sensors, air quality instruments, and corrosion science – and is inventor on around 40 patents. He may be reached at david.williams@ auckland.ac.nz.

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Soc., 145, 2664 (1998).

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Sci., 31, 621 (1990).

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28. S. Hodges, N. J. Laycock, D. P. Krouse, S. Virtanen, P. Schmutz, and M. P. Ryan, J. Electrochem. Soc., 154, C114 (2007).

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34. N. J. Laycock and S. P. White, in Proceedings of CAP 2000, Paper # 43, ACA, Auckland, New Zealand, Nov. 19-22 (2000).

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Sci., 47, 3140 (2005).

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The Electrochemical Society Interface โ ข Winter 2014

THE ELECTROCHEMICAL SOCIETY

MONOGRAPH SERIES

The following volumes are sponsored by ECS, and published

by John Wiley & Sons, Inc. They should be ordered from: electrochem.org/bookstore

Lithium Batteries: Advanced Technologies and Applications Edited by B. Scrosati, K. M. Abraham, W. van Schalkwijk, and J. Hassoun (2013) 392 pages. ISBN 978-1-18365-6 Fuel Cells: Problems and Solutions (2nd Edition)

by V. Bagotsky (2012) 406 pages. ISBN 978-1-1180-8756-5 Uhlig's Corrosion Handbook (3rd Edition)

by R. Winston Revie (2011) 1280 pages. ISBN 978-0-470-08032-0 Modern Electroplating (5th Edition)

by M. Schlesinger and M. Paunovic (2010) 736 pages. ISBN 978-0-470-16778-6 Electrochemical Impedance Spectroscopy

by M. E. Orazem and B. Tribollet (2008) 524 pages. ISBN 978-0-470-04140-6 Fundamentals of Electrochemical Deposition (2nd Edition)

by M. Paunovic and M. Schlesinger (2006) 373 pages. ISBN 978-0-471-71221-3 Fundamentals of Electrochemistry (2nd Edition) Edited by V. S. Bagotsky (2005) 722 pages. ISBN 978-0-471-70058-6 Electrochemical Systems (3rd Edition)

by John Newman and Karen E. Thomas-Alyea (2004) 647 pages. ISBN 978-0-471-47756-3 Atmospheric Corrosion

by C. Leygraf and T. Graedel (2000) 368 pages. ISBN 978-0-471-37219-6 Semiconductor Wafer Bonding

by Q. -Y. Tong and U. Gรถsele (1998) 320 pages. ISBN 978-0-471-57481-1 Corrosion of Stainless Steels (2nd Edition)

by A. J. Sedriks (1996) 464 pages. ISBN 978-0-471-00792-0 ECS Members will receive a discount. See the ECS website for prices.

electrochem.org/bookstore 71

T ECH SEC TION HIGHLIGH NE WS TS Twin Cities On October 3, 2014, the ECS Twin Cities Section held its annual Electrochemistry Symposium. The all-day symposium was well attended with over 96 registrations, and speakers from industry and academia covering a broad range of electrochemical topics.

Approximately 27 attendees were graduate students from Minnesota and the neighboring states, and 16 posters were presented during the afternoon poster session. The free event took place at the 3M Innovation Center and was enjoyed by all.

Speakers and Twin Cities Section Officers at the 2014 Twin Cities Electrochemistry Symposium. Front row: Peter Zhang (Section Vice Chair, Medtronic), Alan Shi (Section Treasurer, Medtronic). Back row: Philippe Buhlmann (Speaker, University of Minnesota), Vincent Chevrier (Section Chair, 3M), Terry Smith (Speaker, 3M), Shawn Kelley (Speaker, Medtronic), Jonathan Tomshine (Speaker, Mayo Clinic), Peter Faguy (Speaker, DoE), Benjamin Wilson (Section Student Representative, University of Minnesota), Darrel Untereker (Speaker, Medtronic), Jagat Singh (Section Secretary, 3M). Missing speakers: Jeff Dahn (Dalhousie University), Andrew Haug (3M). Missing Section Officers: William Howard, Prabhakar Tamirisa (Medtronic).

Europe Section The ECS Europe Section Alessandro Volta Medal Award was established in 1998 and granting of this award is based on outstanding achievements in electrochemical science or solid state technology. This year the award was bestowed on Phil N. Bartlett from the University of Southampton. The awardee presents a lecture at an appropriate symposium during the ECS meeting. Unfortunately, Prof. Bartlett was unable to come to Cancun and will give his presentation in Chicago, May 2015. Therefore, the full information about his accomplishments will be available in the meeting program for spring 2015.

The section elected new officers at the Cancun meeting. They are Chair: Enrico Traversa, King Abdullah University of Science & Technology (KAUST); Vice Chair, Petr Vanýsek, Northern Illinois University (on leave of absence at the Brno University of Technology, Czech Republic); Secretary Renata Solarska, University of Warsaw; and, Treasurer Davide Bonifazi, University of Namur. The past chair is D. Noel Buckley, University of Limerick. Sixteen members-atlarge were also elected to the Executive Committee.

Past Chair of the Europe Section, D. Noel Buckley, inspecting the refreshments at the Cancun meeting. A regular section meeting traditionally occurs at each ECS biannual meeting on Monday evening, and wine and cheese to greet the members is part of the tradition. (Photo P. Vanýsek) 72

The Electrochemical Society Interface • Winter 2014

NE W AWA MEMBERS RDS

ECS Awards & Grants Program:

Call for Nominations

Through our Awards & Grants Program, ECS recognizes outstanding technical achievements in electrochemistry and solid state science and technology. ECS awards are held in high esteem by the scientific community.

Nominating a colleague is a way of highlighting an individualâ&#x20AC;&#x2122;s contribution to our field and shining a spotlight on our ongoing contributions to the sciences around the world.

ECS Awards are open to nominees across four categories: Society Awards, Division Awards, Student Awards, and Section Awards. Specific information for each award, and information regarding rules, past recipients, and nominee requirements are available online. Please note that the nomination material requirements for each award vary.

Email questions to: awards@electrochem.org.

For more about the ECS Awards & Grant Program go to:

electrochem.org/awards

ECS Awards The Edward Goodrich Acheson Award was established in 1928 for distinguished contributions to the advancement of any of the objects, purposes or activities of The Electrochemical Society. The award consists of a gold medal, wall plaque, prize of $10,000, life membership in the Society, and complimentary meeting registration at the meeting to accept the award. The next award will be presented at the PRiME meeting in Honolulu, Hawaii, October 9-14, 2016.

Go to electrochem.org/society to learn more and start the nomination process.

Materials are due by October 1, 2015.

The award of ECS Fellows was established in 1989 for individual contribution and leadership in the achievement of science and technology in the area of electrochemistry and solid state sciences and current active participation of the affairs of ECS, and consists of a scroll, lapel pin, and announcement in a Society publication. Nominations are being accepted for the 2015 class of Fellows, which will be presented at the ECS fall meeting in Phoenix, Arizona, October 11-16, 2015.

Go to electrochem.org/society to learn more and start the nomination process.

Materials are due by February 1, 2015.

The Electrochemical Society Interface â&#x20AC;˘ Winter 2014

The Vittorio de Nora Award was established in 1971 for contributions to the field of electrochemical engineering and technology. The award consists of a gold medal, wall plaque, life membership in the Society, complimentary meeting registration at the meeting to accept the award, and a prize of $7,500.

The next award will be presented at the ECS spring meeting in San Diego, California, May 29-June 3, 2016.

Go to electrochem.org/society to learn more and start the nomination process.

Materials are due by April 15, 2015.

The Henry B. Linford Award for Distinguished Teaching was established in 1981 for excellence in teaching in subject areas of interest to the Society. The award consists of life membership in the Society, a silver medal, wall plaque, complimentary meeting registration at the meeting to accept the award, and a prize of $2,500. The next award will be presented at the ECS spring meeting in San Diego, California, May 29-June 3, 2016.

Go to electrochem.org/society to learn more and start the nomination process.

Materials are due by April 15, 2015. (continued on next page)

73

NE W AWA MEMBERS RDS (continued from previous page) The Charles W. Tobias Young Investigator Award was established in 2003 to recognize outstanding scientific and/or engineering work in fundamental or applied electrochemistry or solidstate science and technology by a young scientist or engineer. The award consists of a scroll, a prize of $5,000, ECS Life Membership, and travel assistance to the meeting of the award presentation (up to $1,000).

Go to electrochem.org/society to learn more and start the nomination process.

Materials are due by October 1, 2015.

Division Awards The Battery Division Research Award was established in 1958 to recognize outstanding contributions to the science and technology of primary and secondary cells and batteries and fuel cells. The award consists of a scroll, a prize of a $2,000, travel assistance to the meeting if required, and membership in the Battery Division for as long as the winner is an ECS member. The next award will be presented at the ECS fall meeting Phoenix, Arizona, October 11-16, 2015.

Go to electrochem.org/division to learn more and start the nomination process.

Materials are due by March 15, 2014.

The Technology Award of the Battery Division was established in 1993 to encourage the development of battery and fuel cell technology. The award consists of a scroll, prize of $2,000, travel assistance to the meeting if required, and membership in the Battery Division for as long as the winner is a Society member. The next award will be presented at the ECS fall meeting in Phoenix, Arizona, October 11-16, 2015.

Go to electrochem.org/division to learn more and start the nomination process.

Materials are due by March 15, 2014.

The Electrodeposition Division Research Award was established in 1979 to recognize recent outstanding achievement or contribution in the field of electrodeposition.

The award consists of a scroll and a prize of $2,000. The next award will be presented at the ECS fall meeting in Phoenix, Arizona, October 11-16, 2015.

Go to electrochem.org/division to learn more and start the nomination process.

Materials are due by April 1, 2015.

The Manuel M. Baizer Award of the Organic and Biological Electrochemistry Division was established in 1992 for outstanding scientific achievements in the electrochemistry of organics. The award consists of a scroll, a prize of $1,000, and travel assistance (if needed) to the meeting where the award presentation will take place. The next award will be presented at the ECS spring meeting in San Diego, California, May 29-June 3, 2016.

Go to electrochem.org/division to learn more and start the nomination process.

Materials are due by January 15, 2015.

74

The Max Bredig Award in Molten Salt and Ionic Liquid Chemistry of the Physical and Analytical Electrochemistry Division was established in 1984 to recognize excellence in molten salt chemistry research and consists of a scroll and a prize of $1,500. The next award will be presented at the PRiME meeting in Honolulu, Hawaii, October 9-14, 2016.

Go to electrochem.org/division to learn more and start the nomination process.

Materials are due by March 1, 2015.

Section Awards The W. Lash Miller Award of the Canada Section was established in 1967 for the excellence of the candidateâ&#x20AC;&#x2122;s publications and/or technical contributions in the field of electrochemical science and technology and/or solid state science and technology. The candidate must have demonstrated independent research in academia, industry or governmental laboratories. To be considered for the award, a nominee must be residing in Canada and have obtained his/her last advanced education degree no more than 15 years before the year of the Award. The recipient does not need to be a member of ECS. The award consists of a prize of $1,000 CAN. The Award will be presented at a meeting of the Canada Section in 2015 during which the award recipient will present a lecture on a subject of major interest to him/ her in the field of electrochemical science and technology and/or solid state science and technology. It may relate to the citation of the Award, or to current activity.

Nominations and supporting documents should be sent to Michael Eikerling, Department of Chemistry, Simon Fraser University, 8888 University Drive, Burnaby, BC, Canada V5A1S6, tel.: 778 782 4463, email: meikerl@sfu.ca. Materials are due by December 31, 2014.

Travel Grants Several of the Societyâ&#x20AC;&#x2122;s Divisions offer travel assistance to students and early career professionals presenting papers at ECS meetings. For details about travel grants for the 227th ECS meeting in Chicago, Illinois, go to electrochem.org/travel_ grants. Please be sure to click on the link for the appropriate Division as each Division requires different materials for travel grant approval prior to completing the online application. You must submit your abstract and have your abstract confirmation number in order to apply for a travel grant. If you have any questions, please email travelgrant@electrochem.org. The deadline for submission for spring 2015 travel grants is January 1, 2015.

The Electrochemical Society Interface â&#x20AC;˘ Winter 2014

NE W MEMBERS ECS is proud to announce the following new members for July, August, and September 2014.

Active Members Joshua Abbott, Marlborough, MA, USA Neil Andrews, Burnaby, BC, Canada David Avison, Woburn, MA, USA Veronica Bedoya, Pflugerville, TX, USA Laura Cabo-Fernandez, Liverpool, Merseyside, United Kingdom Christopher Cordonier, Yokohama, Kanagawa, Japan Achille De Battisti, Ferrara, Italy Francesco Di Franco, Palermo, Italy Anthony Diaz, Ellensburg, WA, USA Peter Dreher, West Chester, OH, USA Giorgio Ercolano, Montpellier Hérault, France Juan Pablo Esquivel, Seattle, WA, USA Isabel Fontinha, Lisbon, Portugal Mary Gladis, Thiruvananthapuram, Kerala, India Myeong Gweon Gu, Yongin Kyunggido, South Korea Liping Guo, DeKalb, IL, USA Tae Hee Han, Seongdong-Gu Seoul, South Korea Mark Hellums, Austin, TX, USA Andriy Hikavvy, Heverlee, Leuven, Belgium Zhen-Dong Huang, Nanjing Jiangsu, P. R. China Mohammed Hussain, Burnaby, BC, Canada M Jayakumar, Chennai Tamil Nadu, India Seungwon Jeon, Gwangju, South Korea Ana Jorge Sobrido, London, London, United Kingdom Rehan Kapadia, Los Angeles, CA, USA Seonghwan Kim, Calgary, AB, Canada Yoshiyuki Kowada, Kato-Shi, Hyogo, Japan Song-Zhu Kure-Chu, Morioka, Iwate, Japan Fredy Kurniawan, Surabaya East Java, Indonesia Rong Lan, Glasgow, United Kingdom Seongsu Lee, Daejeon, South Korea Philip Lees, Boston, MA, USA Xuebin Li, Sunnyvale, CA, USA Ying Li, College Station, TX, USA Shih-Hung Lin, Taichung, Taiwan, Taiwan Omar Lopez-Garrity, Menlo Park, CA, USA Przemyslaw Los, Warsaw, Mazovia, Poland Alex Lugovskoy, Petah-Tiqwah, Israel Ruth Mary, Singapore, Singapore Anca Mazare, Erlangen, Germany Kenneth Mcdonald, Oak Forest, IL, USA Brian Mchugh, Phoenix, AZ, USA Martin Mintchev, Calgary, Canada María Montes De Oca, Distrito Federal, Mexico Siva Nadimpalli, Newark, NJ, USA Ilayaraja Nagarajan, Madurai, Tamil Nadu, Namibia Wako Naoi, Kunitachi, Tokyo, Japan Levent Organ, Istanbul, Turkey Ricardo Orozco-Cruz, Xalapa, Veracruz, Mexico Muzaffer Ozcan, Adana, Turkey Laisa P, Chennai, India Prathap Parameswaran, Tempe, AZ, USA The Electrochemical Society Interface • Winter 2014

Laurent Pilon, Los Angeles, CA, USA Ragupathy Pitchai, Karaikudi, Tamil Nadu, India Carl Ponader, Buford, GA, USA Lauren Powell, Longmart, CO, USA S. Prokes, Washington, DC, USA Jae Hui Rhee, Hwasung Kyunggi, South Korea Eligio Rivero, C.U., Distrito Federal, Mexico Edward Roberts, Calgary, AB, Canada Armando Rojas Hernandez, Hermosillo, Mexico Frances Ross, Yorktown Heights, NY, USA Erik Rosseel, Heverlee, Leuven, Belgium Sujatha Saroj, Thiruvananthapuram Kerala, India Markus Schmuck, Edinburgh Edinburgh, United Kingdom Naoteru Shigekawa, Osaka, Osaka, Japan Yosuke Shimura, Heverlee, Leuven, Belgium Michael Stewart, Washington, DC, USA Gamini Sumanasekera, Louisville, KY, USA Yang Sun, Chandler, AZ, USA Elizabeth Szala, Ijmuiden, Netherlands Isabell Thomann, Houston, TX, USA Zafer Ustundag, Kutahya, Turkey Pradeep Vukkadala, Milpitas, CA, USA Long Wang, Camas, WA, USA Yuxuan Wang, Athens, OH, USA Hiroyasu Watanabe, Battle Creek, MI, USA David Wei, Gainesville, FL, USA Kurt Wostyn, Heverlee, Leuven, Belgium Jie Xiang, San Diego, CA, USA

Member Representatives Kazuki Arihara, Kanagawa, Japan Hayato Chikugo, Kanagawa, Japan Matt Cole, Oak Ridge, TN, USA Hongtao Jia, Tianjin, P. R. China Xueheng Jia, Tianjin, P. R. China Huifen Jin, Tianjin, P. R. China Tomohiro Kaburagi, Yokosuka-Shi, Kanagawa, Japan Lingli Kong, Tianjin, P. R. China Takehiro Maeda, Yokosuka-Shi, Kanagawa, Japan Herve Mouro, Claix, France Takamasa Nakagawa, Yokosuka, Kanagawa, Japan Maren Rastedt, Oldenburg, Germany Jason Scribner, Southern Pines, NC, USA Hang Shi, Tianjin, P. R. China Lisa Uhlig, Oldenburg, Germany Peter Wagner, Oldenburg, Germany Jiang Zhou, Tianjin, P. R. China

Students Selcuk Atalay, Norfolk, VA, USA Sandra Abago, Somerville, MA, USA Amir Abidov, Gumi-Si Gyebngbuk, South Korea Guadalupe Aguilar Lira, México, Hidalgo, Mexico John Ahlfield, Atlanta, GA, USA

Steven Ahn, Providence, RI, USA Chibueze Amanchukwu, Richmond, TX, USA Venu Bandi, Denton, TX, USA Yohe Bando, Sendai, Miyagi, Japan Sriya Banerjee, St Louis, MO, USA Zachary Barton, Champaign, IL, USA Elodie Beche, Grenoble Cedex 9, France Vinith Bejugam, Fayetteville, AR, USA Otavio Beruski, São Carlos, São Paulo, Brazil Benedikt Brandes, Lahstedt, Ni, Germany Yunfei Bu, Atlanta, GA, USA Marthe Emelie Buan, Trondheim SørTrøndelag, Norway Tandeep Chadha, Saint Louis, MO, USA Khushbu Chauhan, Ahmedabad Gujarat, India Tao Chen, Lexington, KY, USA Yiting Chen, Hsinchu, Taiwan, Taiwan Winston Chern, Cambridge, MA, USA Agnieszka Chojnacka, Krakow, Poland Chia Ho Chu, Hsinchu, Taiwan, Taiwan Engin Ciftyurek, Clemson, SC, USA Daniel Cintora, Cordoba, Spain Michael Clark, Edmonton, Canada João Coelho, Dublin, Ireland Oluwaseun Dada, Hong Kong, Hong Kong Andrea De Iacovo, Rome, Italy Julio Donato, Guanajuato, Mexico Zhijia Du, Halifax, NS, Canada Mohammadreza Fazeli, Toronto, ON, Canada Zhange Feng, Copley, OH, USA James Frith, Southampton, Hampshire, United Kingdom Armando Garnica-Rodriguez, Coyoacán, Distrito Federal, Mexico Michael Gerhardt, Cambridge, MA, USA Eleanor Gillette, College Park, MD, USA Paul Gondcharton, Grenoble, France Anju Gopinathan, Bangalore Karnataka, India Perry Grant, Fayetteville, AR, USA Rolf Grieseler, Hinternah, Germany Murside Hacismaloglu, Bursa, Turkey Fudong Han, Greenbelt, MD, USA Yang He, Morgantown, WV, USA Gibran Hernández-Moreno, Puebla, Mexico Nathaniel Hoyt, Cleveland Heights, OH, USA Chen-Pin Hsu, Hsinchu, Taiwan, Taiwan Omar Ibrahim, Surrey, BC, Canada Noramon Intaranont, Southampton, Hampshire, United Kingdom Sijia Jiang, Heverlee, Leuven, Belgium Joel Kamwa, Fayetteville, AR, USA Fatemeh Karimi, Kingston, ON, Canada Jr-Jian Ke, Taipei, Taiwan, Taiwan Minjae Kim, Columbus, OH, USA Soojeong Kim, Ann Arbor, MI, USA Kyle Knust, Bloomington, IN, USA Yun-Hyuk Ko, Seoul, South Korea Michiko Konno, Sendai, Miyagi, Japan Vida Lapornik, Ljubljana, Slovenia Che-Yen Lee, Hsinchu, Taiwan, Taiwan Xuan Liang, College Park, MD, USA Yangang Liang, College Park, MD, USA Kimberly Lincoln, Kennedale, TX, USA (continued on next page) 75

NE W MEMBERS (continued from previous page) Chanyuan Liu, College Park, MD, USA Xi Liu, Hong Kong, Hong Kong Jacob Locke, Southampton, Hampshire, United Kingdom Ersu Lokcu, Eskisehir Odunpazari, Turkey Lan Luo, Raleigh, NC, USA Alexandre Lupien-Bédard, Quebec, QC, Canada Lin Ma, Halifax, NS, Canada Nishant Malik, Oslo, Norway Damien Massy, Grenoble, France Mark Mcarthur, Montreal, QC, Canada Michael Mercer, Stratford-upon-Avon, United Kingdom Michael Metzger, Garching, Bavaria, Germany Angela Mohanty, Clifton Park, NY, USA Sebastien Moitzheim, Heverlee, Leuven, Belgium Diana Morales-Acosta, Ramos Arizpe, Mexico Catherine Munson, Okemos, MI, USA Navaneethan Muthuswamy, Trondheim SørTrøndelag, Norway Manoj Krishna Narayan, Berlin, BE, Germany Kathlyne Nelson, Halifax, NS, Canada Yohei Okada, Yokohama, Kanagawa, Japan Asako Otake, Sendai, Miyagi, Japan Suneesh P V, Coimbatore, Tamil Nadu, India

Michael Palmer, Southampton, Hampshire, United Kingdom Kalani Periyapperuma, Halifax, NS, Canada Rémi Petibon, Dartmouth, NS, Canada Jovan Popovic, Clemson, SC, USA Florian Preishuber-Pfluegl, Graz, St, Austria Brecht Put, Heverlee, Leuven, Belgium Achyut Raghavendra, Clemson, SC, USA Gaddam Rajeshkhanna, India Prakash Ramakrishnan, Daegu, South Korea Gonzalo Ramírez García, León, Guanajuato, Mexico Arun Reddy, Dearborn, MI, USA Marissa Reynolds, Van Buren, AR, USA Philipp Rheinländer, Garching, Germany Carla Robledo, Cordoba, Argentina Meenakshi S, Cuddalore, India Theodore Chandra S, Madurai, Tamil Nadu, India James Saraidaridis, Ann Arbor, MI, USA Biplab Sarkar, Raleigh, NC, USA Maximilian Schwager, Vancouver, BC, Canada Behtash Shakeri, Orono, ME, USA Krishneel Sharma, Suva Rewa Province, Fiji Jamie Shetzline, Central, SC, USA Yadvinder Singh, Surrey, BC, Canada Yuriy Smolin, Philadelphia, PA, USA Patrick Stanley, Riverdale, MD, USA Anthony Stevenson, Nottingham, Notts, United Kingdom

Anthony Stewart, Baker, LA, USA Steven Street, Oldbury, West Midlands, United Kingdom Giwoon Sung, Suwon, South Korea Jianshi Tang, Long Beach, CA, USA James Teherani, Cambridge, MA, USA Saurabh Tembhurne, Lausanne, VD, Switzerland Bingbing Tian, Paris, France Loraine Torres-Castro, San Juan, Puerto Rico Amanda Urcezino, Fortaleza, CE, Brazil Gulin Vardar, Ann Arbor, MI, USA Senthil Velan Venkatesan, Surrey, BC, Canada Laksman Ventrapragada, Clemson, SC, USA Yuta Watanabe, Sendai, Miyagi, Japan Tzu-Chiao Wei, Taipei, Taiwan, Taiwan Daniel Willett, Central, SC, USA Silas Wolff-Goodrich, Martinez, CA, USA Ming Wu, Orsay, France Jian Xia, Halifax, NS, Canada Deijun Xiong, Halifax, NS, Canada Cheng Yang, Charlottesville, VA, USA Xiaoyan Yang, Clemson, SC, USA Rong Ye, Berkeley, CA, USA Tara Yoder, Golden, CO, USA Abm Zakaria, Jackson, MS, USA Xiaowen Zhan, Lexington, KY, USA Xiaowei Zhang, Lexington, KY, USA Lanlan Zhong, Riverside, CA, USA Yumin Zhu, Storrs, CT, USA Tawanda Zimudzi, State College, PA, USA

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electrochem.org/membership/student.html The Electrochemical Society 76

The Electrochemical Society Interface • Winter 2014

2014 ECS Summer Fellowship Reports 2014 Summer Fellowship Committee

Summer Fellowships Each year ECS awards up to five Summer Fellowships to assist students in continuing their graduate work during the summer months in a field of interest to the Society. Congratulations to the five Summer Fellowship recipients for 2014. The Society thanks the Summer Fellowship Committee for their work in reviewing the applications and selecting five excellent recipients. Applications for the 2015 Summer Fellowships are due January 15, 2015 (see http://www.electrochem.org/awards/ student/student_awards.htm#n).

Vimal Chaitanya, Chair New Mexico State University

Peter Mascher McMaster University

Bryan Chin Auburn University

Kalpathy Sundaram University of Central Florida

The 2014 Edward G. Weston Summer Research Fellowship â&#x20AC;&#x201C; Summary Report Electrodeposition of Hybrid Core-Shell Nanowires

by Tuncay Ozel

A

s an environmentally friendly alternative energy conversion device, solar cells are used to convert solar energy into electric current.

Demonstration of electrically and optically favorable, fully absorbing, yet ultrathin semiconductor layers for solar cells is a key scientific challenge.1-4 For example, designing nanowires with a core-shell type semiconductor segment can improve the carrier collection with radial charge separation, whereas integration of plasmonic nanostructures can enhance the photocurrent generation with intensified electric fields.1,4-7 However, a full understanding of the mechanisms behind the electrical and optical enhancement processes is still under debate due to a lack of control over the geometry during the synthesis of nanostructured semiconductor segments and lack of precise integration of the plasmonic structures.

(a)

Herein, we present the electrochemical deposition of light harvesting hybrid coreshell nanowires with plasmonic nanoantenna segments with excellent control over the size and composition of the nanowire segments resulting from the expertise developed in our lab using the on-wire lithography (OWL) technique.8,9 We electrochemically deposited gold and polymerized 3-hexylthiophene (P3HT) segments in porous alumina membranes. While gold is mechanically stable after electrodeposition, vacuum treatment induces isotropic shrinking of the P3HT segment, leaving room around the periphery of the P3HT core for the synthesis of shell segments.10 An n-type cadmium selenide (CdSe) shell was coelectrodeposited using a solution of Cd and Se atoms to create a p-n junction interface.

Finally, a top gold segment was deposited under constant potential. Gold segments

(b)

deposited on both ends of the semiconductor segment serve both as plasmonic antennas and metallic leads for electrical characterization. A scanning transmission electron microscope image (top) and simulated electric field intensity maps (bottom) of a typical nanowire (diameter: ~74 nm) are presented in Fig. 1a. Simulation results highlighted the intensity and position of the localized electric fields around the core-shell semiconductor segment.

Experimentally measured extinction spectra of such nanowires dispersed in solution showed two distinct plasmon resonances, demonstrating the tunability of the plasmonic antenna resonance wavelength by tailoring the length of the gold nanorods on opposite sides of the semiconductor segment (Fig. 1b). Emission intensity of the P3HT core considerably dropped as the (continued on next page)

(c)

Fig. 1. (a) Scanning transmission electron microscope image (scale bar equals to 50 nm), and electric field intensity maps (recorded at 600 nm 1170 nm) of a hybrid core-shell nanowire. (b) Experimental extinction spectrum, and (c) emission spectra of the nanowires dispersed in solution.

The Electrochemical Society Interface â&#x20AC;˘ Winter 2014

77

Ozel

(continued from previous page)

CdSe shell segment was removed selectively, signifying the advantageous optical properties of depositing the shell segment (Fig. 1c). Additionally, the current-voltage characteristics of a single nanowire device (diameter: ~280 nm) showed significant photocurrent generation under illumination (Fig. 2), with a notable ~125 fold on/off ratio (under 30 mW/cm2 excitation at 3 V potential bias), demonstrating the functionality of the nanowires prepared using this method.

In summary, our method of template assisted electrodeposition of multisegmented core-shell nanowires via polymer shrinking creates a platform to synthesize the next generation of plasmon enhanced selfstanding nanoelectronic devices such as photodetectors, solar cells, and light emitting diodes. We expect this synthetic capability to be very useful for exploring novel plasmonically enhanced nanoelectronic devices.

Acknowledgments I would like to thank The Electrochemical Society for this summer fellowship and Prof.

Chad A. Mirkin for his guidance and support in conducting this research.

About the Author Tuncay Ozel is currently pursuing a PhD under the supervision of Prof. Chad Mirkin, in the Department of Materials Science and Engineering at Northwestern University, IL. His thesis project focuses on the integration of plasmonic nanostructures into coaxial nanowires to study fundamental light-matter interactions and fabricate optoelectronic devices for nanophotonic applications. He may be reached at ozel@u.northwestern.edu.

Fig. 2. Electrical characterization of a hybrid core-shell nanowire with and without illumination.

References 1. C. E. Garnett, M. L. Brongersma, Y. Cui, M. D. McGehee,. Annu. Rev. Mater. Res. 41, 269 (2011).

2. J. Tang, Z. Huo, S. Brittman, H. Gao, P. Yang, Nature Nanotech. 6, 568 (2011).

3. A. S. Arico, P. Bruce, B. Scrosati, J. M. Tarascon, W. van Schalkwijk, Nature Mater. 4, 366 (2005).

4. H. A. Atwater, A. Polman, Nature Mater.

9, 205 (2010).

5. N. C. Lindquist, W. A. Luhman, S. H. Oh and R. J. Holmes, Appl. Phys. Lett.

93, 123308 (2008).

6. S. Linic, P. Christopher, D. B. Ingram, Nature Mater. 10, 911 (2011).

7. S. Brittman, H. Gao, E. C. Garnett, P. Yang, Nano Lett. 11, 5189 (2011).

8. L. Qin, S. Park, L. Huang, C. A. Mirkin, Science 309, 113 (2005).

9. M. J. Banholzer, L. Qin, J. E. Millstone, K. D. Osberg, C. A. Mirkin, Nat. Protoc.

4, 838 (2009).

10. T. Ozel, G. R. Bourret, A. L. Schmucker, K. A. Brown, C. A. Mirkin, Adv. Mater.

25, 4515 (2013).

ECS celebrates the many successful achievements of members of the electrochemical and solid state science community.

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The Electrochemical Society Interface â&#x20AC;˘ Winter 2014

The 2014 Colin G. Fink Summer Research Fellowship – Summary Report Advanced Microfluidic Pumping at Poly(3,4-ethylenedioxythiophene)Modified Electrodes via AC-Magnetohydrodynamics

by Christena K. Nash

A

p aradigm shift in microfluidic pumping using redox-magnetohydrodynamics (MHD) that preserves its advantages and resolves problems that previously slowed its application in analytical chemistry (for pumping small volumes and sustaining fluid flow) is demonstrated herein.

Miniaturization of chemical analysis for labon-a-chip (LOAC) devices offers portability and automation with less power, reagent and waste volumes, and analysis time. A crucial feature is the programmable manipulation of fluid within the device. MHD microfluidics

can provide continuous pumping without channels or moving parts and can stop or reverse fluid flow without the need for valves by switching off or changing the sign of the ionic current, respectively.1 The magnetohydrodynamic force, FB (N∙m−3), and therefore fluid flow, is generated by the ionic current density, j (C∙s−1∙m−2), when perpendicular to a magnetic field, B (T), and follows the right-hand rule according to the cross-product relationship, FB = j × B.2- 5 In previous studies, we have shown that electrodes modified with poly(3,4ethylenedioxythiophene) (PEDOT) are

Fig. 1. (a) Photograph of the microelectrode array chip showing electrode features and dimensions.

Expanded images show unmodified gold and PEDOT-modified gold band electrodes as viewed under a microscope. During the AC MHD experiments, electrode set 1 (working), and sets 2 and 3 (combined auxiliary/quasi-reference) were active. Set 1 was oppositely biased from sets 2 and 3. (b) Fluid flow profile based on bead speeds in the 5600 µm gap between PEDOT-modified microband electrodes. Error bars represent ± one standard deviation. (c) Particle image velocimetry (PIV) data from which points in (b) were obtained. (d) Vectors involved in AC-MHD for synchronized electrical and magnetic fields to maintain flow in a single direction.

The Electrochemical Society Interface • Winter 2014

capable of high currents while limiting the interaction with the sample, thus improving compatibility. However, use of PEDOTmodified electrodes limits redox-MHD pumping to short times because it cannot sustain the current once charge transfer in the film is completed, unlike diffusionlimited redox species in solution. The device used in this study takes advantage of the highly reversible nature of PEDOT to sustain redox-MHD over indefinitely long periods by recycling PEDOT in real time.

This study used an array chip with microband and microdisk-ring electrodes (Fig. 1) and a solution confined over them with a gasket and lid. Polystyrene latex beads (10 µm) added to the electrolyte solution allowed visualization of fluid movement using video microscopy. The chip was placed on an electromagnet with a magnetic field (0.033 T RMS) perpendicular to the chip. The electrodes were modified with a conducting polymer, PEDOT, instead of redox species added to solution, to generate an ionic current from the electrochemical reaction at the films, avoiding bubble formation and electrode corrosion.

Synchronized sinusoidal potential waveforms applied to PEDOTmodified electrodes (producing an AC current) and the electromagnet (producing an AC magnetic field) allowed continuous pumping in a single direction while charging and discharging the films. Only 10 Hz was needed, drastically minimizing heating compared to prior AC MHD studies, while generating high currents. The resulting fluid velocity (115 µm s−1) and flat flow profile between the PEDOT-modified band electrodes are comparable to those under DC conditions, when redox species are present in solution.6 Spiraling fluid flow with a speed as high as 350 µm∙s−1 (Fig. 2) at PEDOTmodified concentric disk-ring electrodes attained 10 times the speed achieved with redox species in solution previously, and holds promise for mixing applications.7 In this study, a new microfluidic technique, AC redox-MHD, was investigated that sustains linear and rotational microfluidic pumping through synchronized variations in ionic current, generated by PEDOTmodified electrodes, and the magnetic field, generated by an electromagnet. Future work will focus on using AC redox-MHD in labon-a-chip applications. (continued on next page) 79

Nash

(continued from previous page)

Acknowledgments The author thanks ECS for the Colin Garfield Fink Summer Fellowship and Ingrid Fritsch for guidance through the project. In addition, the author expresses gratitude to Jerry Homesley for extensive discussions in designing the electronics for the power amplifier and electromagnet. Additional support was provided by the National Science Foundation (NSF) (CBET-1336853).

About the Author Christena Nash recently defended her dissertation, Modified-Electrodes for RedoxMagnetohydrodynamic (MHD) Pumping for Microfluidic Applications. She received her doctorate from the University of Arkansas under the direction of Ingrid Fritsch. She may be contacted at cknash5@gmail.com.

References 1. E. C. Anderson, M. C. Weston, and I. Fritsch, Analytical Chemistry 82 2643 (2010).

2. M. C. Weston, M. D. Gerner, and I. Fritsch, Analytical Chemistry 82 3411 (2010).

3. S. R. Ragsdale, J. Lee, and H. S. White, Analytical Chemistry 69 2070 (1997).

4. N. Leventis and X. Gao, The Journal of Physical Chemistry B 103 5832 (1999).

5. N. Leventis, J. Phys. Chem. B 102 3512 (1998).

6. V. Sahore and I. Fritsch, Analytical Chemistry 85 11809 (2013).

7. V. Sahore and I. Fritsch, Microfluidics and Nanofluidics, DOI 10.1007/s10404014-1427-6 (2014).

Fig. 2. (a) Schematic of the rotational flow concept with a PIV image of fluid flow recorded around the disk electrode at 150 Âľm above the chip. During AC MHD experiments, the disk and ring electrodes were both active, but oppositely biased. (b) Contour plot of magnitude of velocity (its direction is shown in (a)) reveals the flow profile around the disk electrode throughout the height of the cell.

80

The Electrochemical Society Interface â&#x20AC;˘ Winter 2014

The 2014 Joseph W. Richards Summer Research Fellowship â&#x20AC;&#x201C; Summary Report Thermogalvanic Waste Heat Recovery in Transportation Energy Systems

by Andrey Gunawan

W

(continued on next page)

The Electrochemical Society Interface â&#x20AC;˘ Winter 2014

Fig 1. 3D CAD drawings of the wind tunnel and the cross-sectional diagram of the annular Cu/Cu2+ thermogalvanic cell.

# ! !"

$ !% Č?

aste heat recovery remains an inviting subject for research.

Solid state thermoelectric devices have been widely investigated for this purpose, but their practical application remains challenging due to high cost and the inability to fabricate them in geometries that are easily compatible with heat sources.

An alternative to solid-state thermoelectric devices are thermogalvanic cells.1-7 The temperature difference between the hot and the cold electrodes creates a difference in electrochemical potential of the redox couples at the electrodes. Once connected to a load, electrical current and power is delivered, converting thermal energy into electrical energy. The aim of this summer project is to extend ongoing research to study the feasibility of incorporating thermogalvanic systems into automobiles.

A climate-controlled wind tunnel (Fig. 1) was built to provide equivalent conditions to the ambient air stream under the car.

Temperature was controlled using a window air conditioner, while an air mover drove the flow up to 6 m sâ&#x2C6;&#x2019;1. A heat gun provided the equivalent of a low-temperature exhaust gas stream (~110Â oC). The annular cell was bound by concentric copper pipes (electrodes) and CPVC bulkheads; all sealed with silicone. K-type thermocouples were attached with epoxy onto electrode surfaces to measure the electrode temperature, which were monitored and recorded by a Campbell Scientific CR23X Micrologger.

The cell potential (E) was probed using a Fluke 8846A Digital Multimeter. An Elenco RS-500 resistor box (Rext) was connected in parallel to measure power output, P = E2/Rext.

A 0.7 M CuSO4 aqueous electrolyte was used, with 0.1 M H2SO4 as the supporting electrolyte. The Tcold was varied based on the quad-monthly average ambient air temperature (Tambient) in Phoenix, AZ of 31.6, 22.5, and 14.1Â oC. Because thermal resistance from the hot air stream to the inner copper pipe is large relative to the thermal resistance of the cell, the Thot was measured to be less than the hot air streamâ&#x20AC;&#x2122;s temperature. Reducing this resistance would greatly improve the system performance.

The experimental values of Thot and Tcold are shown next to their resultant plots in Fig. 2.

These results showed that higher Tambient yielded a higher P, because of the higher average cell temperature, Tavg = (Thot+ Tcold)/2. This trend agreed with our previous study.8 Since the resistor could only be

!

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Fig 2. Power density vs. current density curves for the annular Cu/Cu2+ thermogalvanic cell tested at the three ambient temperatures of (a) 31.6, (b) 22.5, and (c) 14.1Â oC. Thot and Tcold are the temperatures of the hot and cold electrodes, respectively, as shown in Fig. 1. The inset shows historical data of average ambient air temperature in Greater Phoenix area, AZ from July 1, 2013 to June 30, 2014, which is imported from the Arizona State University Weather Station;9 solid and dotted lines indicate bi-monthly and quad-monthly average air temperatures, respectively.

81

Gunawan

(continued from previous page)

varied down to 1.1 Ω, we could not show the maximum power output (Pmax) for Tambient values of 31.6 and 22.5 oC. Nevertheless, the magnitude of the P and Pmax was consistent with our previous observations.1,8 We have demonstrated that the liquid electrolyte enables a thermogalvanic device to conform to the shape of automotive exhaust pipes much more readily than a solid-state thermoelectric device. Expensive, cleanroombased manufacturing processes are not required for constructing the cell, resulting in potentially lower production costs than high-performance solid-state thermoelectrics.

Future studies will focus on improving the experimental setup by enhancing the airside heat transfer, incorporating a flow cell, and increasing the electrode surface area to increase the sites available for reaction, thereby helping generate more power.

Acknowledgment

References

The author gratefully acknowledges ECS for the Joseph W. Richards Summer Fellowship and Professor Patrick Phelan for his invaluable support and guidance throughout the project. In addition, the author wishes to thank Professor Candace Chan for her steadfast encouragement and recommendation in earning this fellowship, Nicholas Fette for his great assistance and fruitful discussions on the project, and Professor Daniel Buttry for all helpful conversations and suggestions regarding the electrochemistry aspect of the project.

Additional support from the National Science Foundation through Award CBET-1236571 is also gratefully acknowledged.

1. A. Gunawan, C.-H. Lin, D. A. Buttry, V. Mujica, R. A. Taylor, R. S. Prasher and P. E. Phelan, Nanoscale and Microscale Thermophys. Eng., 17, 304 (2013).

2. T. I. Quickenden and Y. Mua, J. Electrochem. Soc., 142, 3985 (1995).

3. N. Jiao, T. J. Abraham, D. R. MacFarlane and J. M. Pringle, J. Electrochem. Soc., 161, D3061 (2014).

4. Y. Yamato, Y. Katayama and T. Miura, J. Electrochem. Soc., 160, H309 (2013).

5. P. F. Salazar, S. Kumar and B. A. Cola, J. Electrochem. Soc., 159, B483 (2012).

6. N. S. Hudak and G. G. Amatucci, J. Electrochem. Soc., 158, A572 (2011).

7. T. Murakami, T. Nishikiori, T. Nohira and Y. Ito, J. Electrochem. Soc., 150, A928 (2003).

8. A. Gunawan, H. Li, C.-H. Lin, D. A. Buttry, V. Mujica, R. A. Taylor, R. S. Prasher and P. E. Phelan, Int. J. of Heat Mass Transf., 78, 423 (2014).

9. Arizona State University, “ASU Weather Station,” Ameresco, 2014, http://cm.asu. edu/weather/. (Accessed 1 June 2014.)

About the Author Andrey Gunawan is a PhD candidate in Mechanical Engineering at Arizona State University under the direction of Professor Patrick Phelan. He may be reached at andreygu@asu.edu or at www. andreygunawan.com

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82

The Electrochemical Society Interface • Winter 2014

The 2014 F. M. Becket Summer Research Fellowship – Summary Report Support@Platinum - Nanoparticle Electrocatalytic Nanobowls

by Brandy Kinkead Pilapil

E

lectrocatalytic materials have become increasingly important over the past decade owing to their broad applicability to low emission and emission-free energy technologies, including fuel cell technology. Platinum is a great electrocatalyst due its generally good stability, high surface energy, electronic structure and interfacial properties.1-5 The morphology and chemical environment of Pt can have a substantial effect on its catalytic performance.2-7 Presently, carbon (C) black (high surface area C particles) is the most commonly used support for Pt nanoparticle (NP) electrocatalysts in low temperature polymer electrolyte membrane fuel cells (PEMFCs).4 This support provides a high surface area for dispersion of the Pt NPs and good electrical conductivity. Weak interaction between Pt NPs and the C support and oxidation of the C support under harsh fuel cell operating conditions leads to a loss of Pt catalysts and subsequent decrease in fuel cell performance. Alternative supports, such as metal oxides, are being pursued to improve the performance of fuel cell catalyst layers by increasing the stability of the Pt catalysts through favorable support interactions.6,7 This can increase the device lifetime and reduce the overall cost of the PEMFC.

The preparation of a new catalyst layer design that contained Pt NPs supported on metal or metal oxide nanobowls (NBs) was pursued in this study. These materials are hereafter referred to as support@ PtNP NBs. A modular sacrificial template method (Scheme 1) was used to prepare the support@PtNP NBs.8-11 This new catalyst layer design offered a number of advantages over designs containing Pt NPs dispersed onto C black. These include: 1) optimization of catalyst-support interactions by tuning the composition of the support material; 2) fine tuning control over the distribution of Pt NPs over the surfaces of the NBs to mitigate degradation via aggregation and/or agglomeration; and 3) promoting porosity of the catalyst layer through the 3D morphology of the NB supports, which could improve reactant/product transport for efficient catalytic turnover.5 It was envisaged that these materials could also provide further insight into NP-support interactions through the preparation of materials that only differ in the support material composition, while maintaining the NP-support morphology (e.g., porosity of catalyst layer, Pt NP size and Pt NP distribution).

Using the described method, TiOx@PtNP NBs were prepared and characterized by electron microscopy (EM) (Fig. 1). Energy dispersive X-ray spectroscopy elemental maps (Fig. 1d) revealed that the Pt NPs were well dispersed over the inner surfaces of the TiOx NB support. Nanobowl electrodes were also prepared by dispersing the NBs in Nafion® and casting the resulting catalyst suspension onto polished glassy carbon disks. The bowl-like shape of the NBs can be clearly seen in scanning EM images (Fig. 1e). Electrochemical characterization of this material, and preparation and characterization of other support@PtNP NB materials will be detailed in a subsequent report.

This new method for the preparation of supported nano-Pt catalysts could be readily expanded into other materials. The possible ability to easily tune electrochemical stability and activity of the Pt NPs by varying interactions with the support enables support@PtNP electrocatalytic nanobowls to have great potential for a variety of applications. (continued on next page)

Scheme 1. Schematic describing the modular sacrificial template method used in the preparation of support@PtNP nanobowls. (a) Pt nanoparticle (NP) decorated polystyrene (PS) spheres are assembled onto a Si wafer.8 (b) The support material of interest is coated onto the surface of the assembled PS spheres using physical vapour deposition. (c) Pt NP decorated PS spheres with a partial coating of support material are released from the Si wafer support by sonication.7 (d) PS is dissolved in organic solvents under reflux conditions to reveal support@PtNP nanobowls.

The Electrochemical Society Interface • Winter 2014

83

Pilapil

(continued from previous page)

Acknowledgments I would like to thank The Electrochemical Society, the Natural Sciences and Engineering Research Council of Canada and my advisor, Dr. Byron Gates, for supporting this research.

I would also like to thank Austin Lee, who has assisted in NB materials preparation.

About the Author Brandy Kinkead Pilapil currently is in the process of completing her doctorate at Simon Fraser University in the Department of Chemistry under the supervision of Dr. Byron Gates. She may be reached at bkinkead@sfu.ca.

References 1. B. E. Conway and G. Jerkiewicz, Electrochimica Acta, 45, 4075 (2000).

2. B. E. Hayden, Accounts of Chemical Research, 46, 1858 (2013).

3. M. Nesselberger, M. Roefzaad, R. Faycal Hamou, P. Ulrich Biedermann, F. F. Schweinberger, S. Kunz, K. Schloegl, G. K. H. Wiberg, S. Ashton, U. Heiz, K. J. J. Mayrhofer and M. Arenz, Nature Materials, 12, 919 (2013).

4. M. K. Debe, ECS Trans., 45(2), 47 (2012).

5. O.-H. Kim, Y.-H. Cho, S. H. Kang, H.-Y. Park, M. Kim, J. W. Lim, D. Y. Chung, M. J. Lee, H. Choe and Y.-E. Sung, Nature Communications, 4, 2473 (2013).

6. Y.-J. Wang, D. P. Wilkinson and J. Zhang, Chem. Rev. 111, 7625 (2011) 7. S. Y. Huang, P. Ganesan, W. S. Jung, N. Cadirov, and B. N. Popov, ECS Trans., 33(1), 483 (2010) 8. J. C. Love, B. D. Gates, D. B. Wolfe, K. E. Paul and G. M. Whitesides, Nano Letters, 2, 891(2002) 9. M. Xu, N. Lu, H. Xu, D. Qi, Y. Wang and L. Chi, Langmuir, 25, 11216 (2009) 10. B. Kinkead, M. C. P. Wang, M. T. Y. Paul, A. Nazemi and B. D. Gates, submitted.

11. B. Kinkead, A. Ali, J. C. Boyer and B. D. Gates, Mater. Res. Soc. Symp. Proc., 1546, L001 (2013).

84

Fig 1. Electron microscopy analysis of TiOx@PtNP nanobowls. (a) Transmission electron microscopy (TEM) image of Pt NP decorated PS sphere template. (b) TEM image of Pt NP decorated PS sphere template partially coated with TiOx. (c) Scanning TEM (STEM) image of TiOx@PtNP nanobowls. (d) Energy dispersive X-ray spectroscopy elemental map of a TiOx@PtNP nanobowl (as seen in (c) using STEM). (e) Scanning electron microscope image of a region of a TiOx@PtNP nanobowl electrode dispersed with Nafion polymer.

The Electrochemical Society Interface â&#x20AC;˘ Winter 2014

The 2014 H. H. Uhlig Summer Research Fellowship – Summary Report How Do Cyclic Carbonate Electrolyte Additives Improve Li-ion Battery Performance?

by Hadi Tavassol

L

i ion batteries (LIB) are ubiquitous in portable electronics, and are increasingly used in automotive applications. Improvements in stability and long-term capacity of LIBs are essential to satisfy fast growing demands in both sectors. The electrolyte mixture in a LIB is often modified to boost the long term stability of the solid electrolyte interphase (SEI) which forms particularly at the surface of the battery anode. Small quantities of additives are known to increase the stability and long-term cyclability of LIBs.1,2 Some of the most widely used additives are cyclic carbonates such as vinylene carbonate (VC) and vinyl ethylene carbonate (VEC). This class of additives contain unsaturated C-C bonds, which are believed to facilitate the formation of a more stable SEI.

The exact mechanism of additive activity and their effect on the properties of the SEI remains unknown. The SEI is thought to consist of an inner inorganic part with an outer organic layer, likely formed via oligomerization of the solvent,3,4 the existence of which changes the mechanical properties of the electrode.5 The additives may change the SEI formation mechanism.6 Here we investigated the effect of added VC and VEC molecules on the SEI. We used an Au model anode system in a 1 M LiClO4/propylene carbonate electrolyte solution, with and without added additive.

Electrochemical analysis of the Au anode in the presence of low (0.2 %, v/v) and high (2.0 %) concentrations of the VC and VEC additives was performed in two different potential regions: between 3 V (vs. Li+/0) and

0.25 V (Fig. 1a), and between 3.0 V and 0.15 V (Fig. 1b), where bulk lithiation occurred.

In the absence of additives, early reductive features corresponding to the irreversible reduction of electrolyte components appeared at around 2.25 V. The presence of the additives caused only minor changes in the 1st cycle of the voltammogram. As bulk lithiation occurred, two major effects were evident: i) as the concentration of the additive increased, an overpotential in the onset of the bulk lithiation was observed, this effect was more pronounced with VEC; and, ii) addition of VEC and VC increased the maximum current observed during lithiation. (continued on next page)

Fig. 1. Electrochemical analysis of additive containing electrolytes using cyclic voltammetry at 1 mV s−1 in 1M LiClO4/PC with varying amount of VC and VEC additives. (a) Cyclic voltammetry of the 3 V (vs. Li+/0) to 0.25 V region, and (b) 3.0 V to 0.15 V region, the insets show the onset of the bulk lithiation.

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Tavassol

(continued from previous page)

These observations led us to probe the physical properties of the SEI using an electrochemical quartz crystal microbalance (Fig. 2). Changes in the mass of the electrode during cycling are shown in Fig. 2a. The residual mass (δ Δm) at the end of each cycle is a good estimate of the SEI mass. As expected, SEI mass increased with cycling in all electrolyte solutions. The major effect in the presence of the additives was the decrease in the magnitude of the SEI mass with extended cycling, relative to the additive-free case.

We also measured the motional resistance (Rm) of the QCM electrode. Rm is linearly related to (ρη)1/2,7 where ρ and η are respectively the density and viscosity of the film on the electrode surface. The residual motional resistance (δRm) is the change in Rm from cycle to cycle. At the end of the 1st cycle, the δRm from all additive containing electrolytes (Fig. 2b) pointed towards increased motional resistance, indicating that the presence of additive molecules increased the (ρη)1/2 which is proportional to film rigidity. The δRm of the VC containing electrolytes reached steady state after only three cycles, while VEC-containing and additive-free electrolyte continue to evolve with cycling. After 7 cycles the electrolyte solution with VEC showed the highest δRm, followed by additive-free electrolyte and VC-containing electrolyte. Addition of VC decreased film rigidity. Interestingly, VCcontaining solutions exhibited the highest lithiation currents (Fig. 1b), possibly as a consequence of a more porous and Liconductive SEI film. This study indicates that additives improve the performance of the LIB in part by modifying the physical state of the SEI.

Acknowledgments The ECS is gratefully acknowledged for the H. H. Uhlig Summer Fellowship Award.

I would also like to thank Professor Andrew A. Gewirth for his constant guidance and support. This work was supported in part by the Center for Electrical Energy Storage, an Energy Frontier Research Center funded by the U.S. Department of Energy. I also acknowledge Jennifer L. Esbenshade, my collaborator in this project.

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Fig 2.(a) Mass changes with cycling in different electrolyte mixtures, small solid circles indicate the residual mass at the end of each cycle (δΔm). (b) Changes in the motional resistance (δRm) of the film with cycling.

About the Author

References

Hadi Tavassol received his PhD in Analytical Chemistry from University of Illinois at Urbana-Champaign in August 2014. He completed his thesis under the supervision of Professor Andrew A. Gewirth studying Interfacial Process in Li-ion Batteries. He is currently a Postdoctoral Scholar at the California Institute of Technology working with Professor Sossina M. Haile. He may be reached at hadit@caltech.edu.

1.

D. Aurbach, K. Gamolsky, B. Markovsky, Y. Gofer, M. Schmidt, and U. Heider, Electrochimica Acta, 47, 1423 (2002).

2. L. Chen, K. Wang, X. Xie, and J. Xie, Journal of Power Sources, 174, 538 (2007).

3. H. Tavassol, J. W. Buthker, G. A. Ferguson, L. A. Curtiss, and A. A. Gewirth, J. Electrochem. Soc., 159, A730 (2012).

4. D. Bar-Tow, E. Peled, and L. Burstein, J. Electrochem. Soc., 146, 824 (1999).

5. H. Tavassol, M. K. Y. Chan, M. G. Catarello, J. Greeley, D. G. Cahill, and A. A. Gewirth, J. Electrochem. Soc., 160, A888 (2013).

6. K. Ushirogata, K. Sodeyama, Y. Okuno, and Y. Tateyama, J. Am. Chem. Soc., 135, 11967 (2013).

7. S. J. Martin, J. J. Spates, K. O. Wessendorf, T. W. Schneider, and R. J. Huber, R. J. Anal. Chem., 69, 2050 (1997).

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Cancun Student Poster Session Award Winners Students presenting their posters in Cancun were entered into a competition and had their work judged. There were 86 submissions.

The winners were announced on Wednesday evening at the meeting, and ECS President Paul Kohl handed out the prizes.

First Place, Electrochemical Science & Technology, Poster #2196: “Effect of the Components of the Electrode on the Morphological and Electrochemical Performance of Manganese Dioxide-Based Electrode for Application in Hybrid Electrochemical Capacitor,” Axel Gambou-Bosca, Université du Québec à Montréal; Daniel Belanger, adviser.

Second Place, Electrochemical Science & Technology, Poster #2221: “Electrochemical Dechlorination of 2-Chlorophenol on Ti-Ni, Ti-Pd and Ti-Ni-Pd Electrodes,” Miguel Angel Arellano Gonzalez, Universidad Autónoma Metropolitana-Iztapalapa; Ignacio González Martinez and Anne-Claire Texier, advisers.

First Place, Solid State Science & Technology, Poster # 2194: “Pulsed Electrodeposition for Preparing Hollow, Conical Needles with Sub-Micron Dimensions,” Andrew Durney and Elizabeth Hotvedt, University of Rochester; H. Mukaibo, adviser.

Second Place, Solid State Science & Technology, Poster #2245: “Thin Films and Superlattices in the Bi-Fe-O System Prepared by ALD,” Andrew R. Akbashev, Drexel University; Jonathan E. Spanier, adviser.

The General Student Poster Session in Cancun was organized by Venkat Subramanian, Christopher Johnson, Rene Lara-Castro, Kalpathy Sundaram, Vimal Chaitanya, Pallavi Pharkaya, Matt Foley, and Ajit Khosla.

The session also requires intense efforts of the judges, who, in Cancun, included Stefan De Gendt, Julien Durst, Paul Gannon, Andrew Herring, Andrew Hoff, Oana Leonte, Shirley Meng, Yaw Obeng, Alice Suroviec, Raluca Van Staden, and Natasha Vasiljevic.

ECS President Paul Kohl presented awards to the winners of the Student Poster Session competition in Cancun. From left to right are: Andrew R. Akbashev (Second Place, Solid State Science & Technology); ECS President Paul Kohl; Axel Gambou-Bosca (First Place, Electrochemical Science & Technology); and Andrew Durney (First Place, Solid State Science & Technology).

Brno University of Technology Student Chapter The Student Chapter associated with the Brno University of Technology in the Czech Republic was founded on October 9, 2006, and is one of the older Student Chapters of ECS. The present member leadership is currently in its third year of activities. The current members are Jiří Libich, Tomáš Kazda, Ondřej Čech, Josef Máca, Michal Musil and David Pléha. The research interests of this group are related to modern battery studies, such as aprotic and polymer-gel electrolytes, negative and positive and general electrode materials for lithium-ion batteries, including such systems as lithium-sulfur and materials such as spinned nanowires.

The members participated actively individually and collectively on various presentations of their results. One notable participation was at the 35th meeting on The Unconventional Sources of Electric Energy (NZEE) held May 21-23 in Blansko, Czech Republic. The other was the second annual meeting of the Student Chapter, held in July in the town of Sloup. Also significant was the participation at the 15th International Conference on Batteries and Accumulators (ABAF) in Brno, Czech Republic. This is an international meeting, which took place this year August 24-28. This meeting was co-sponsored

by The Electrochemical Society and a volume of ECS Transactions from this meeting will be published. The student chapter members, in addition to their poster presentations and participation at the meeting presentations, were also involved in helping with organizational aspects of the meeting.

The Electrochemical Society Interface • Winter 2014

Two members of the Brno University of Technology Student Chapter at the poster session of the 15th International Conference on Batteries and Accumulators (ABAF) in Brno, Czech Republic, Tomáš Kazda (left) and Jiří Libich (right) with Petr Vanýsek, co-editor of Interface, who also participated.

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Drexel University Student Chapter

Dalian University of Technology research group with Boris Dyatkin of Drexel University (third row, third from right).

As a representative of the ECS Student Chapter at Drexel University, Boris Dyatkin, Treasurer of the Chapter, was part of a recent international visiting researcher fellowship (from the International Center of Materials Research, University of California – Santa Barbara) that spent eight weeks at Dalian University of Technology in Dalian, China. Dyatkin conducted several activities that promoted information exchange, among them was a tutorial on proper electrochemical methods, including 2-electrode vs.

3-electrode tests, proper reference/counter electrode methods, and

impedance spectroscopy. He also gave a talk to the research group of Prof. Jieshan (Jason) Qui of the Carbon Research Laboratory on the implementation of carbon in electrochemistry.

Dyatkin also visited the East China University of Science and Technology (ECUST) in Shanghai, where he met with representatives considering the establishment of a formalized ECS Student Chapter at ECUST. In addition to delivering a talk to the group led by Prof.

Wenmin Qiao on carbon in electrochemistry and a novel in situ FTIR/ Spectroelectrochemistry approach, he hosted a Q&A panel on proper electrochemistry technique and analysis methods.

Students on the

Look Out !

We want to hear from you!

Students are an important part of the ECS family and the future of the electrochemistry and solid state science community . . .

• What’s going on in your Student Chapter?

• What’s the chatter among your colleagues?

• What’s the word on research projects and papers?

• Who’s due congratulations for winning an award?

Send your news and a few good pictures to interface@electrochem.org.

We’ll spread the word around the Society. Plus, your Student Chapter may also be featured in an upcoming issue of Interface!

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Atlanta Student Chapter at Georgia Tech The ECS Atlanta Student Chapter at Georgia Institute of Technology organized a grill-out to welcome new students and widely publicize its presence across campus on the cozy afternoon of September 25th. More than 100 students participated and enjoyed the late September Atlanta weather with burgers, hot dogs, and edifying conversation. Every semester, several events are scheduled for all interested students and researchers in the Atlanta area, including lectures, company demonstrations, and social events. Once a year, the Chapter plans the Georgia Section Regional Meeting together with the faculty, inviting students from across the southeast. The group is currently run under the leadership of graduate students Enbo Zhao

(President), Naoki Nitta (Vice President), Liang He (Secretary), Rajiv Jaini (Treasurer), and Tim Lin (Socials Chair). Peter Hesketh is the advisor to this chapter.

For the rest of the semester, talks are planned for Hailong Chen from Georgia Tech and Michael Hickner from the Pennsylvania State University. The Georgia Section Regional Meeting is scheduled for the spring, and will include a poster competition with cash prizes for the best posters. Researchers from across the region are invited to attend. Further information will be posted when available on our website at https://sites.google.com/site/ecsatgt/.

Grilling at Georgia Tech.

Officers of the Atlanta Student Chapter at Georgia Tech: (left to right) Rajiv Jaini, Treasurer; Naoki Nitta, Vice President; Tim Lin, Socials Chair, Enbo Zhao, President; and Liang He; Secretary.

Research Triangle Student Chapter The past few months have been very busy for the ECS Research Triangle Student Chapter. Its primary focus has been to bring members together and foster opportunities for student researchers from UNC, Duke, and NC State by collaborating with other local student organizations. In a chapter members highlight, they partnered with students from the Materials Research Society chapters to organize an exciting Triangle Student Research Competition (TSRC). This event incorporated both poster presentations and live technology demonstrations to showcase the cutting edge research done by undergraduate and graduate students from all across the Research Triangle. In addition, in an effort to boost the presence of STEM in the local communities, all participants were asked to make a donation towards local student-led organization named SciRen in lieu of a registration fee. In the end, over 120 students, professors, and industry representatives packed into the symposium, which was held at the Research Triangle Park Headquarters. The large turnout enabled a successful night full of networking, ideas for collaboration, and an increase in ECS student chapter membership. Furthermore, thanks to a collaborative fundraising effort across the universities, winners of the event were awarded cash prizes, free ECS Conference

Students explore ongoing research from Duke, UNC, and NC State at the poster presentation of the Triangle Student Research Competition.

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registration fees, and even a full travel grant to showcase their demo to companies on the national stage at a Technology Innovation Forum.

The Research Triangle Student Chapter also had representatives at the fall ECS Meeting in Cancun in October 2014. The chapter chair, Isvar Cordova, presented his work on solar fuels and supercapacitors, while Marty Dufficy presented his research on “Alginate Nanofibers as a Binder in Lithium-Ion Cells Lithium-Ion Batteries.” The Research Triangle Student Chapter has also begun working with other organizations to establish a recurring seminar series, through which they plan on hosting esteemed ECS researchers starting next semester.

Attendees check out the demo presentations during the Triangle Student Research Competition.

Officers of the Research Triangle Student Chapter at the Triangle Student Research Competition, from left to right: Dominica Wong (UNC), James Daubert (NCSU), Isvar Cordova (Duke), and Marty Dufficy (NCSU).

Research Triangle Student Chapter President Isvar Cordova at Chichén Itzá in Mexico after the ECS Cancun meeting.

University of Maryland Student Chapter

UMD Student Chapter members in the Nizuc lobby at the Moon Palace resort in Cancun, Mexico.

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To begin the new semester, the University of Maryland (UMD) Student Chapter held a poster contest on August 15th, with the winners receiving travel assistance to the ECS Fall Meeting in Cancun. Six students presented their research to a panel of faculty judges who evaluated the presentation quality. All of the students had impressive research topics spanning a wide array of energy conversion and storage topics. Many presentations focused on aspects of solid oxide fuel cells (SOFC) or batteries with Yi-Lin Huang taking first place for his presentation on “Manganese Implantation into Low Temperature SOFC Cathodes.” Second place was a tie between former chapter president, Colin Gore, and Chanyuan Liu. Colin’s poster detailed his research on mechanical and electrical properties of ceramic anodes and Chanyuan’s research focused on a nanopore battery array structures. Chris Pellegrinelli, Alex Pearse, and Jiayu Wan also received travel assistance for the conference.

The UMD Student Chapter participated in this year’s 226th Meeting of the Electrochemical Society in Cancun, Mexico, sending 11 student members to give oral The Electrochemical Society Interface • Winter 2014

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UMD Student Chapter members outside University of Maryland Energy Research Center.

presentations. Our high attendance was thanks in large part to six student travel grants we were able to award from our 2012 Outstanding Student Chapter Award funding and to the ECS travel grants our members also won. We were proud to have such a large cohort at the meeting to accept the 2nd Place award for the Outstanding Student Chapter in 2013. At the meeting, our members enjoyed the Sunday Evening Get Together where they were able to network with founders of small companies, professors, and ECS Fellows in a casual setting.

We also developed new professional collaborations and friendships and had a great time meeting other student members of ECS at the Student Mixer. In the symposia, our members’ interests ranged from lithium ion batteries to solid oxide fuel cells to the energy water nexus.

As presenters, we gained valuable insight from leaders; as audience members we learned new approaches and realized new directions for research. The presentations and the evening poster sessions were a unique opportunity to engage in conversations with other scientists in our fields.

University of Texas at Austin Student Chapter Since 2007, the ECS Student Chapter at The University of Texas at Austin (UT-Austin) has carried out its commitment towards promoting solid state and electrochemical sciences by organizing several technical and non-technical talks, networking events, and outreach activities throughout the course of each year. Additionally, the Student Chapter provides support to other events organized by the Center for Electrochemistry, Texas Materials Institute, and the Cockrell School of Engineering at UT-Austin. Our member base includes undergraduate, graduate, and post-doctoral researchers from a diverse range of academic disciplines including chemistry, physics, and materials science; along with members studying mechanical, chemical, electrical, and biomedical engineering.

The UT-Austin Student Chapter has hosted several faculty presentations and student chalk talks over the last few years and has participated in many outreach events such as the annual UT-Austin open-house event, Explore UT. These events have allowed members to share cutting-edge research across different disciplines within and outside the UT-Austin community. This fall semester has brought about the expansion of the ECS Student Chapter into new events and activities.

The UT-Austin ECS Student Chapter was fortunate to host a Q&A session with David Walt of Tufts University, founder of Illumina and Quanterix, two companies developing important diagnostic methods

David Walt giving entrepreneur advice on “How to Take Academic Research to Industrial Commercialization.”

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for the life sciences that have made a significant societal impact in recent years. Dr. Walt led a discussion with our members about the commercialization of academic research. He shared with us the challenges faced while managing time between his academic lab and starting up a new company. Dr. Walt also stressed the importance of the partnerships he established with people of high business acumen.

The UT-Austin Student Chapter has recently begun volunteering with SciBridge to help achieve the goal of building strong connections between scientists in Africa and the United States. The first stage of the project was to assemble, test, and distribute sustainable energy experiment kits (dye-sensitized solar cells) to African universities, with the purpose of the kits being to serve as interactive educational tools. It has been immensely rewarding to work with SciBridge towards this endeavor. The first experiment kits have been shipped to Makerere University in Uganda and we are looking forward to

UT-Austin Student Chapter members making and testing dye-sensitized solar cell experiment kits with SciBridge. From left to right: Anthony Dylla, Tyler Mefford, Veronica Augustyn (co-founder of SciBridge), and Josephine Cunningham.

receiving feedback. The SciBridge project is made possible by the Materials Research Society (MRS) Foundation Grassroots Grant Award and the solar cell experiment was designed by the University of California, Los Angeles. For more information visit www.

SciBridge.org.

The UT-Austin Student Chapter received the ECS Outstanding Student Chapter Award for 2014. We would like to thank The Electrochemical Society for initiating the Student Chapter Program and funding our events, our previous Student Chapter officers (Preethi Mathew, Netzahualcoyotl Curras, and Karen Scida), and the Student Chapter members for making the Chapter what it is, and Arumugam Manthiram (Director of the Texas Materials Institute at UT-Austin), the faculty advisor of the ECS Student Chapter at UTAustin, for his constant and continued support.

More information about the ECS Student Chapter at UT-Austin can be found at www.ECSStud.com.

The 2014 Outstanding Student Chapter Award Plaque with (front row, left to right) Arumugam Manthiram, UT-Austin Student Chapter Faculty Advisor; Josephine Cunningham, Chapter President; and Donald Robinson Chapter Vice-President; and student members (back row, left to right) Matthew West, Daeil Yoon, Ke-Yu Lai, and Benjamin Weaver.

University of Virginia Student Chapter

Students and faculty attending a seminar with guest speaker Jason Lee giving his talk.

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The newly reinvigorated University of Virginia Student Chapter is proud to report on the successful launch of its seminar series in July 2014. With the help of Robert G. Kelly, the chapter hosted their inaugural speaker, Raul B. Rebak from GE Global Research in Schenectady, NY. Dr. Rebak presented his work on “Electrochemical Processes Controlling Localized Corrosion in Passivating Nickel Alloys.” His presentation showcased how the corrosive or inhibiting processes associated with nickel alloy electrochemistry are dictated by the alloys inherent metallurgy and characteristic electrochemical parameters, as well as by the species present in the aqueous environment in contact with the alloy.

More recently, the chapter organized a second seminar with guest speaker Jason S. Lee from the Naval Research Laboratory in The John C. Stennis Space Center, Mississippi. Dr. Lee was invited to present a seminar

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Members of the University of Virginia ECS Student Chapter with associated faculty members and the ECS seminar speaker (from left): Gilbert Liu, Jay Srinivasan, Pierce Robinson, Scott Lee, Raul B. Rebak (GE Global Research), Robert G. Kelly (ECS National Capital Section Vice-Chair and Professor, Materials Science and Engineering), Richard P. Gangloff (Professor, Materials Science and Engineering), Michael Nguyen, Noelle Co, Mary Lyn Lim.

highlighting his work on microbiologically influenced corrosion (MIC). Although the topic was new to many of the members, Dr. Lee’s presentation on the issues and challenges encountered in the diagnostic, monitoring, and mitigation of MIC sparked great interest.

Both seminars were well-received and brought students and faculty from various departments such as Chemistry, Chemical Engineering, Electrical and Computer Engineering, and Materials Science and

Start

Engineering. Students and faculty also had the opportunity to meet and discuss with both speakers prior to and after their respective seminars, which initiated possible collaborations. The success of these events fueled the enthusiasm of the chapter’s resident members, and prompted an additional seminar scheduled for November 3rd.

For this seminar, the chapter hosted Eric Wachsman, an ECS fellow, from the University of Maryland.

Advertisers Index

a Student Chapter!

ECS currently has 40 student chapters around the world, which provide students an opportunity to gain a greater understanding of electrochemical and solid-state science, to have a venue for meeting fellow students, and to receive recognition for their organized scholarly activities. Students interested in starting a student chapter may contact membership@electrochem.org for details.

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T ST ECH UDENT HIGHLIGH NE WS TS Student Awards

ECS Student Awards & Fellowship Program:

Call for Nominations For more about the ECS Awards & Fellowship Program go to:

electrochem.org/awards

ECS student awards and fellowships are open to anyone who meets the ECS criteria for being a student. Specific information for each award, and information regarding rules, past recipients, and nominee requirements are available online. Please note that the nomination material requirements for each award vary.

The ECS Summer Fellowships were established in 1928 to assist students during the summer months in pursuit of work in the field of interest to ECS. The next fellowships will be presented in 2015.

Go to electrochem.org/society to learn more and start the nomination process.

Materials are due by January 15, 2015.

The ECS Outstanding Student Chapter Award replaced the Gwendolyn Wood Section Excellence Award, and was established in 2012 to recognize outstanding ECS Student Chapters. Up to three winners will be selected. One Outstanding Student Chapter will be selected with the winner receiving $1,000, and recognition with a plaque and chapter group photo in Interface. One or two additional Student Chapters may be selected as runners-up, and designated as Chapters of Excellence. Recognition certificates will be mailed to the Chapters of Excellence. The next awards will be presented in 2015.

Go to electrochem.org/student to learn more and start the nomination process.

Materials are due by March 31, 2015.

The Student Research Award of the Battery Division was established in 1962 to recognize promising young engineers and scientists in the field of electrochemical power sources and consists of a scroll, a prize of $1,000, waiver for the meeting registration, travel assistance to the meeting if required, and membership in the Battery Division as long as a Society member. The next award will be presented at the ECS fall meeting in Phoenix, Arizona, October 11-16, 2015.

Go to electrochem.org/student to learn more and start the nomination process.

Materials are due by March 15, 2015.

The Canada Section Student Award was established in 1987 for a student pursuing, at a Canadian University, an advanced degree in any area of science or engineering in which electrochemistry is the 94

ECS provides a number of fellowships and awards to help students in our field become full-fledged professionals. This is an amazing opportunity to recognize and boost the career of the hard working students you know.

Find out more about summer fellowships, awarded student membership, student division and section awards, and more.

Email questions to: awards@electrochem.org.

central consideration. The award consists of consists of a monetary award determined by the Section Executive Committee not to exceed $1,500 US. The next award will be presented at a meeting of the Canada Section in 2015.

Go to electrochem.org/student to learn more and start the nomination process.

Materials are due by February 28, 2015.

Student Travel Grants Several of the Societyâ&#x20AC;&#x2122;s Divisions offer travel assistance to students and early career professionals presenting papers at ECS meetings. For details about travel grants for the 227th ECS meeting in Chicago, Illinois, please see the Chicago Call for Papers; or visit the ECS website: electrochem.org/student/ travelgrants.htm. Please be sure to click on the link for the appropriate Division as each Division requires different materials for travel grant approval prior to completing the online application. You must submit your abstract and have your abstract confirmation number in order to apply for a travel grant. If you have any questions, please email travelgrant@electrochem.org. The deadline for submission for spring 2015 travel grants is January 1, 2015.

Awarded Student Memberships Available ECS Divisions are offering Awarded Student Memberships to qualified full-time students. To be eligible, students must be in their final two years of an undergraduate program or enrolled in a graduate program in science, engineering, or education (with a science or engineering degree). Postdoctoral students are not eligible. Awarded memberships are renewable for up to four years; applicants must reapply each year. Memberships include article pack access to the ECS Digital Library, and a subscription to Interface. To apply for an Awarded Student Membership go to electrochem.org/ student.

The Electrochemical Society Interface â&#x20AC;˘ Winter 2014

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General Topics Batteries and Energy Storage Carbon Nanostructures and Devices Corrosion Science and Technology Dielectric Science and Materials Electrochemical/Electroless Deposition Electrochemical Engineering Electronic Materials and Processing Electronic and Photonic Devices and Systems Fuel Cells, Electrolyzers, and Energy Conversion Organic and Bioelectrochemistry Physical and Analytical Electrochemistry, Electrocatalysis, and Photoelectrochemistry Sensors

CHICAGO

Important Deadlines • Discounted hotel rates start at $189 and are available now at the meeting headquarters hotel, the Hilton, Chicago. The reservation deadline is April 24, 2015 or until the block sells out, reserve early!

• Early-bird registration opens in January 2015, early-bird pricing available through April 24, 2015.

• Take advantage of exhibition and sponsorship opportunities, submit your application by February 20, 2015.

• Travel grants are available for student attendees and young professional (early career and faculty) attendees. Please use the online submission system which may be found by visiting: electrochem.org/sponsorship/ travel_grants.htm, applications are due January 1, 2015.

The 227th ECS Meeting will be held at the Hilton Chicago, 720 South Michigan Avenue, Chicago, Illinois, 60605, USA. Please visit the Chicago Meeting page for the most up-to-date information on hotel accommodations, registration, short courses, special events and to review the online technical program. Full papers presented at ECS meetings will be published in ECS Transactions.

electrochem.org/chicago

The Electrochemical Society Interface • Winter 2014

SAVE THE DATE

• • • • • • • • • • • •

Photo taken in 1998 by Wikipedia user Soakologist. No rights claimed or reserved.

May 24-28, 2015

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ECS Institutional Members

(Number in parentheses indicates years of membership)

The Electrochemical Society values the support of our institutional members. Institutional members help ECS support scientific education, sustainability and innovation. ECS recognizes their incredible work and generosity. Through ongoing partnership, ECS will continue to lead as the advocate, guardian, and facilitator of electrochemical and solid state science and technology.

Visionary AMETEK – Scientific Instruments (33) Oak Ridge, TN, USA

Benefactor Asahi Kasei E-Materials Corporation (6) Chiyoda-Ku, Japan Bio-Logic USA Knoxville, TN, USA, Bio-Logic SAS (6) Claix, France Duracell (57) Bethel, CT, USA Gamry Instruments (7) Warminster, PA, USA Gelest Inc. (5) Morrisville, PA, USA Hydro-Québec (7) Varennes, Canada Industrie De Nora S.p.A. (31) Milano, Italy Metrohm Autolab, Ultrecht, Netherlands, Metrohm USA (8) Westbury, NY, USA Saft Batteries, Specialty Battery Group (32) Cockeysville, MD, USA Scribner Associates Inc. (18) Southern Pines, NC, USA

Patron El-Cell (1) Hamburg, Germany Energizer (69) Westlake, OH, USA Faraday Technology, Inc. (8) Clayton, OH, USA IBM Corporation (57) Yorktown Heights, NY, USA

Lawrence Berkeley National Lab (10) Berkeley, CA, USA Panasonic Corporation (7) Osaka, Japan Pine Research Instrumentation (8) Durham, NC, USA Toyota Research Institute of North America (8) Ann Arbor, MI, USA

Sponsoring Axiall Corporation (19) Monroeville, PA, USA Central Electrochemical Research Institute (21) Tamilnadu, India C. Uyemura & Co., Ltd. (18) Osaka, Japan EaglePicher Technologies, LLC (7) Joplin, MO, USA Electrosynthesis Company, Inc. (18) Lancaster, NY, USA Ford Motor Company (1) Dearborn, MI, USA GS-Yuasa International Ltd. (34) Kyoto, Japan Honda R&D Co., Ltd. (7) Tochigi, Japan Medtronic, Inc. (34) Minneapolis, MN, USA Next Energy EWE – Forschungzentrum (6) Oldenburg, Germany Nissan Motor Co., Ltd. (7) Yokosuka, Japan

Permascand AB (11) Ljungaverk, Sweden Quallion, LLC (14) Sylmar, CA, USA TDK Corporation, Device Development Center (21) Narita, Japan Technic, Inc. (18) Providence, RI, USA Teledyne Energy Systems, Inc. (15) Sparks, MD, USA Tianjin Battery Joint-Stock Co., Ltd (1) Tianjin, China TIMCAL Ltd. (27) Bodio, Switzerland Toyota Central R&D Labs., Inc. (34) Nagoya, Japan Yeager Center for Electrochemical Sciences (16) Cleveland, OH ZSW (10) Ulm, Germany

Sustaining 3M Company (25) St. Paul, MN, USA Co-Operative Plating Company, (3) St. Paul, MN, USA General Motors Research Laboratories (62) Warren, MI, USA Giner, Inc./GES (27) Auburndale, MA, USA International Lead Zinc Research Organization (35) Durham, NC, USA Johnson Controls Advanced Power Solutions GmbH (30) Amtsgericht, Hannover, Germany

Kanto Chemical Co., Inc., (2) Soka City, Saitama, Japan

Leclanche SA (29) Yverdon, Switzerland Los Alamos National Laboratory (6) Los Alamos, NM, USA Mitsubishi Heavy Industries, Ltd. (1) Nagasaki, Japan Occidental Chemical Corporation (72) Dallas, TX, USA Reagent (2) Runcorn, Cheshire, England Sandia National Labs (38) Albuquerque, NM, USA SanDisk (1) Tokyo, Japan SolviCore GmbH & Co. KG (1) Hanau-Wolfgang, Germany

Please help us continue the vital work of ECS by joining as an institutional member today. To join or discuss institutional membership options please contact Dan Fatton, Director of Development, at 609.737.1902 ext. 115 or dan.fatton@electrochem.org.

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The Electrochemical Society Interface • Winter 2014

C all f o r p ap er s Photo by

oenix.

©Visit Ph

228th ECS Meeting

Phoenix, AZ October 11-16, 2015

t Phoenix.

Photo by ©Visi

The Electrochemical Society Interface • Winter 2014 Photo by ©Visit Phoenix.

Hyatt Regency Phoenix & Phoenix Convention Center

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228th ECS Meeting

Phoenix, AZ October 11-16, 2015

CALL FOR PAPERS Photo by

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For all details about the 228th Meeting in Phoenix, please visit www.electrochem.org.

For the full Phoenix Call for Papers, see www.electrochem.org/meetings/biannual/228/.

General Information

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he 228th ECS Meeting will be held October 11-16, 2015. This major international conference offers a unique blend of electrochemical and solid state science and technology; and serves as a major forum for the discussion of interdisciplinary research from around the world through a variety of formats, such as oral presentations, poster sessions, exhibits, and tutorial sessions.

Abstract Submission and Deadlines

Submit one original meeting abstract electronically via the ECS website, no later than May 1, 2015. Please carefully check the symposium listings for any alternate abstract submission deadlines. For complete details on abstract submission and symposium topics, please see www.electrochem.org/meetings/biannual/228/.

Faxed abstracts, e-mailed abstracts, and late abstracts will not be accepted. In June 2015, all presenting authors will receive an e-mail notifying them of the date, time, and location of their presentation. Other hardcopy letters will be sent only upon request to abstracts@electrochem.org.

Meeting abstracts should explicitly state objectives, new results, and conclusions or significance of the work. Regardless of whether you submit as a poster or an oral presentation, it is at the symposium organizers’ discretion whether it is scheduled for an oral or poster presentation. Programming for this meeting will occur in June 2015.

Paper Presentation

All authors selected for either oral or poster presentations will be notified in June 2015. Oral presentations must be in English. Both LCD projectors and laptops will be provided for oral presentations. Presenting authors MUST bring their presentation on a USB flash drive to be used with the laptop that will be provided in each technical session room. If a presenting author would like to use his/her own laptop for presentation, we strongly suggest that the author verify laptop/projector compatibility in the presentation room prior to the start of the session or all other presentations. Speakers requiring additional equipment must make written request to the ECS headquarters office at least one month prior to the meeting and appropriate arrangements will be worked out, subject to availability, and at the expense of the author. Poster presentations should be displayed in English, on a board approximately 3 feet 10 inches high by 3 feet 10 inches wide (1.17 meters high by 1.17 meters wide), corresponding to the abstract number and day of presentation in the final program.

Manuscript Publication

ECS Meeting Abstracts—All meeting abstracts will be published on the ECS website, copyrighted by ECS, and all abstracts become the property of ECS upon presentation.

ECS Transactions—All full papers and posters presented at ECS meetings are eligible for submission to the online proceedings publication, ECS Transactions (ECST). The degree of review to be given each paper is at the discretion of the symposium organizers.

Some symposia will publish an “enhanced” issue of ECST, which will be available for sale at the meeting and through the ECS Digital Library. Please see each individual symposium listing in the full Call for Papers to determine if there will be an “enhanced” ECST issue. In the case of symposia publishing “enhanced” issues, submission of a full-text manuscript to ECST is mandatory and required in advance of the meeting.

Some symposia will publish a “standard” issue of ECST for which all authors are encouraged to submit their full-text papers. Please see each individual symposium listing in the full Call for Papers to determine if there will be a “standard” ECST issue. Upon completion of the review process, papers from the “standard” issues will be published shortly after their acceptance. Once published, papers will be available for sale through the ECS Digital Library.

Please visit the ECST website (ecsdl.org/ECST/) for additional information, including overall guidelines, deadlines for submissions and reviews, author and editor instructions, a manuscript template, and more.

Authors presenting papers at ECS meetings, and submitting to ECST, are also encouraged to submit to the Society’s technical journals: the Journal of The Electrochemical Society, ECS Journal of Solid State Science and Technology, ECS Electrochemistry Letters, or ECS Solid State Letters. Although there is no hard deadline for the submission of these papers, it is considered that six months from the date of the symposium is sufficient time to revise a paper to meet the stricter criteria of the journals. “Instructions to Authors” are available from the ECS website.

Authors now have the choice of publishing their research as Open Access in the ECS journals. Attendees of the 228th ECS Meeting will receive one Article Credit (for use for up to 12 months after the meeting) to be used in place of payment of the Article Processing Charge, normally USD $800. For more information about Open Access at ECS, please see http://www.electrochem.org/oa.

If publication is desired elsewhere after presentation, written permission from ECS is required.

Financial Assistance

Financial assistance is very limited and generally governed by the symposium organizers. Individuals may inquire directly to the organizers of the symposium in which they are presenting their paper to see if funding is available. For details, please see http://www.electrochem.org/sponsorship/travel_grants.htm.

Letter of Invitation

Individuals requiring an official letter of invitation should write to the ECS headquarters office; such letters will not imply any financial responsibility of ECS.

Hotel Reservations — Deadline September 11, 2015

The 228th ECS Meeting will be held at the Phoenix Convention Center and the Hyatt Regency Phoenix. Please refer to the meeting website for the most up-to-date information on hotel availability and information about the blocks of rooms where special rates have been reserved for participants attending the meeting. The hotel reservation deadline is September 11, 2015.

Meeting Registration

All participants—including authors and invited speakers—are required to pay the appropriate registration fees. Hotel and meeting registration information will be posted on the ECS website as it becomes available. The deadline for discounted early-bird registration is September 11, 2015.

Short Courses

A number of short courses will be offered on Sunday, October 11, 2015 from 9:00 AM-4:30 PM. Short Courses require advance registration and may be cancelled if enrollments are too low. As of press time, the following Short Courses are planned for the meeting: Basic Impedance Spectroscopy, Fundamentals of Electrochemistry, Basic Corrosion, Grid Scale Energy Storage, and PE Fuel Cells. Please check the ECS website for the final list of offerings.

Technical Exhibit

The 228th ECS Meeting in Phoenix will include a Technical Exhibit, featuring presentations and displays by over 40 manufacturers of instruments, materials, systems, publications, and software of interest to meeting attendees. Coffee breaks are scheduled in the exhibit hall along with evening poster sessions.

Sponsorship Opportunities

ECS biannual meetings offer a wonderful opportunity to market your organization through sponsorship. Sponsorship opportunities include unparalleled benefits and provide an extraordinary chance to present scientific products and services to key constituents from around the world. Sponsorship allows exposure to key industry decision makers, the development of collaborative partnerships, and potential business leads. ECS welcomes support in the form of general sponsorship at various levels: Platinum: $10,000+, Gold: $5,000, Silver: $3,000, and Bronze: $1,500.

Sponsors will be recognized by level in Interface, the Meeting Program, meeting signage, and on the ECS website. In addition, sponsorships are available for the plenary and keynote talks and other special events. These opportunities include additional recognition, and may be customized to create personalized packages. Special event sponsorships will be assigned by the Society on a first-come, first served basis. Advertising opportunities—in the Meeting Program as well as in Interface— are also available. Please contact Becca Jensen Compton at 1.609.737.1902, ext.

102 for further details.

Contact Information

If you have any questions or require additional information, contact ECS, 65 South Main Street, Pennington, New Jersey, 08534-2839, USA, tel: 1.609.737.1902, fax: 1.609.737.2743, e-mail: meetings@electrochem.org; Web: www.electrochem.org.

228th ECS Meeting

Phoenix, AZ October 11-16, 2015

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Symposium Topics A — Batteries and Energy Storage A01 — Joint General Session: Batteries and Energy Storage -and- Fuel Cells, Electrolytes, and Energy Conversion A02 —Batteries - Theory, Modeling, and Simulation A03 —Batteries Beyond Lithium-Ion A04 — Battery Safety A05 — Electrolytes and Electrochemical Interfaces in Energy Storage Systems A06 — High-Energy Li-Ion Intercalation Materials A07 — Intermetallic Anodes A08 — Materials and Cell Designs for Flexible Energy Storage and Conversion Devices A09 — Recent Advances in Supercapacitors B — Carbon Nanostructures and Devices B01 —Carbon Nanostructures: Fullerenes to Graphene C — Corrosion Science and Technology C01 —Corrosion General Poster Session C02 — Coating and Surface Modification for Corrosion Protection C03 — Contemporary Aspects of Corrosion and Protection of Magnesium and Its Alloys C04 — Corrosion Numerical Modeling 2 C05 — Critical Factors in Localized Corrosion 8 C06 — Pits & Pores 6: Nanomaterials, In Memory of Yukio H. Ogata D — Dielectric Science and Materials D01 —Nanocrystal-embedded Dielectrics for Electronic and Photonic Devices D02 — Nonvolatile Memories D03 — Photovoltaics for the 21st Century 11 D04 — Semiconductors, Dielectrics, and Metals for Nanoelectronics 13 E — Electrochemical/Electroless Deposition E01 —Current Trends in Electrodeposition - An Invited Symposium E02 — Fundamentals of Electrochemical Growth and Surface Limited Deposition E03 — Novel Design and Electrodeposition Modalities 2 E04 — Semiconductors, Metal Oxides, and Composites: Metallization and Electrodeposition of Thin Films and Nanostructures 3 F — Electrochemical Engineering

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G — Electronic Materials and Processing G01 —Atomic Layer Deposition Applications 11 G02 — Semiconductor Cleaning Science and Technology 14 (SCST 14) G03 — Thermoelectric and Thermal Interface Materials 2 G04 — ULSI Process Integration 9 G05 — GaN & SiC Power Technologies 5 H — Electronic and Photonic Devices and Systems H01 —Low-dimensional Nanoscale Electronic and Photonic Devices 8 H02 — Solid-State Electronics and Photonics in Biology and Medicine 2 H03 — State-of-the-Art Program on Compound Semiconductors 58 (SOTAPOCS 58) I — Fuel Cells, Electrolyzers, and Energy Conversion I01 —Concentrated Solar Energy Conversion & Storage I02 — Harnessing Multi-Step Electrochemical Reactions for Energy Conversion and Storage I03 — High Temperature Experimental Techniques and Measurements 2 I04 — Ionic Conducting Oxide Thin Films I05 — Polymer Electrolyte Fuel Cells 15 (PEFC 15) J — Luminescence and Display Materials, Devices, and Processing J01 —Physics and Chemistry of Luminescent Materials L — Physical and Analytical Electrochemistry, Electrocatalysis, and Photoelectrochemistry L01 — Physical and Analytical Electrochemistry, Electrocatalysis, and Photoelectrochemistry General Session L02 — Charge Transfer in Biological Systems 2 L03 — Electroactive and Redox Active Polymers L04 — Electrode Processes 10 L05 — Nanoscale Electrochemistry L06 — Photocatalysts, Photoelectrochemical Cells, and Solar Fuels 6 L07 — Physical and Analytical Electrochemistry in Ionic Liquids 4 L08 —Single Particle/Molecule Electrochemical Detection M — Sensors M01—Sensors, Actuators, and Microsystems General Session

F01 —Electrochemical Engineering General Session

M02—New Paradigms in Sensor Technology

F02 — Industrial Opportunities and Challenges in Electrochemical Engineering

M03—Sensors for Agriculture

F03 — Membrane-based Electrochemical Separations

Z — General Z01 —General Society Student Poster Session Z02 —Nanotechnology General Session Z03 —Impedance Technologies, Diagnostics, and Sensing Applications

The Electrochemical Society Interface • Winter 2014

99

All photos © Glasgow City Marketing Bureau.

ECS Conference on Electrochemical Energy Conversion & Storage with SOFC-XIV July 26-31, 2015

GLASGOW Scotland

Scottish Exhibition and Conference Center

General Information This international conference convening in Glasgow, July 26-31, 2015, is devoted to the following areas: • Section A: Solid Oxide Fuel Cells (SOFC-XIV)—All aspects of research, development, and engineering of solid oxide fuel cells. Lead organizer: Subhash C. Singhal, Pacific Northwest National Laboratory.

• Section B: Batteries—A wide range of topics related to battery technologies. Lead organizer: Peter G. Bruce, Oxford University.

• Section C: Low Temperature Fuel Cells—Low-temperature fuel cells, electrolyzers, and redox flow cells. Lead organizer: Hubert A. Gasteiger, Technische Universität München, Germany.

This is the first of a series of planned biennial conferences in Europe by The Electrochemical Society on electrochemical energy conversion/storage materials, concepts, and systems, with the intent to bring together scientists and engineers to discuss both fundamental advances and engineering innovations. The conference will start with a reception on Sunday evening, and presentations will be scheduled from Monday through Friday.

Important Deadlines • Submit your abstract no later than February 20, 2015 • Discounted hotel options are available now until June 15, 2015 or until the blocks sell out, reserve early!

• Early-bird registration opens in March 2015, early-bird pricing available through June 15, 2015.

• Take advantage of exhibition and sponsorship opportunities, submit your application by April 24, 2015.

Please visit the Glasgow Meeting page for the most up-to-date information most up-to-date information regarding hotel accommodations, registration, short courses, special events and to review the online technical program.

electrochem.org/glasgow

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