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www.materialstoday.com NOVEMBER 2009 | VOLUME 12 | NUMBER 11 Energy uncovered Reactor design and modelling,
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NOVEMBER 2009 | VOLUME 12 | NUMBER 11

Energy uncovered

Reactor design and modelling, the new blue print

Available online at

12 | NUMBER 11 Energy uncovered Reactor design and modelling, the new blue print Available online

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Polymers Displays Dielectrics Ceramics Impedance Z real Mott Schottky Semiconductors Nanotechnology 1 C 2
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Impedance
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Solar cells
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imagZ
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IMPEDANCE
CELLSSOLAR
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EDITORIAL

Energy crisis

ISSN 1369-7021 Journal number: 03069 EDITORIAL Energy crisis Can fusion and fission harness a new hope

Can fusion and fission harness a new hope for our energy needs?

Jonathan Agbenyega | Editor, Materials Today | j.agbenye@elsevier.com

This month we take a look at some of the fascinating developments in the world of nuclear fission and fusion and issues that have plagued scientists for years. We’ll also take a look at how some of these developments will impact on our overall energy usage through the 21 st Century and beyond.

You cannot pick up a paper or turn on the radio without hearing some reference to our environment; greenhouse gases, sustainable energy sources, etc. As a nation we are becoming increasingly aware of the challenges facing our world and the consequences if we do not change our

energy consumption patterns.

The challenge facing us today is not only in finding suitable

ways to control and harness the energy but to create

commercially viable routes to suit our consumption needs.

At the moment there is somewhere in the region of over 430 nuclear fission reactors in the world providing about 15% of the worlds supply of electricity. Research has

improved the overall efficiency of these reactors but there

are still many hurdles to jump in finally building reactors that will withstand the ever stringent safety tests being employed.

Fusion power is also not without its challenges; we are currently witnessing a surge in interest and investment in looking at how fusion can assist in not only commercial power generating plants but also in military applications.

Whatever the outcome we are on route to uncover some

fundamental issues around energy and how materials used to contain these reactions behave.

Editorial Advisory Panel

Gabriel Aeppli University College London, UK Caroline Baillie Queens University, Canada Zhenan Bao Stanford University, USA Franco Cacialli University College London, UK Martin Castell University of Oxford, UK Peter Goodhew University of Liverpool, UK

Ulrich Gösele Max Planck Institute of Microstructure Physics, Germany Hermann Grimmeiss Lunds Universitet, Sweden Alan Heeger University of California, Santa Barbara, USA Mark Johnson Naval Research Laboratory, USA Richard A. L. Jones University of Sheffield, UK

Our first paper takes on this very theme, Steven Zinkle and Jeremy Busby from Oak Ridge National Laboratory

present a fascinating review on structural materials used in

a number of situations for fission and fusion energy.

The discovery and design of nuclear fuels is discussed

in our second paper, the author Marius Stan walks us

through the multi scale models and simulations used to predict irradiation effects on properties such as thermal conductivity, oxygen diffusivity, and thermal expansion.

Atomic scale probing, and modelling can provide a greater understanding of how materials behave in some of the conditions found in fission and fusion reactors, Emmanuelle Marquis et al., from the University of Oxford and National Nuclear Laboratory elaborate.

The science of plasma facing materials for fusion power is an important area of research and D. Duffy at UCL expands on some of the challenges and breakthroughs here.

M. Samaras from the Paul Scherrer institute looks at bubble nucleation and growth, reviewing some of the modelling paradigms used to understand the mechanisms involved.

Our final paper from Ramirez- Cusesta et al., looks at some of the fundamental properties of hydrogen storage and the design of new hydrogen storage materials.

storage and the design of new hydrogen storage materials. Neil McKeown Cardiff University, UK Tae Won

Neil McKeown Cardiff University, UK Tae Won Noh Seoul National University, Korea Stephen Pearton University of Florida, USA Marshall Stoneham FRS University College London, UK Helena Van Swygenhoven Paul Scherrer Institute, Switzerland Richard Vaia Air Force Research Laboratory, USA

George Whitesides Harvard University, USA Jackie Yi-Ru Ying Institute of Bioengineering and Nanotechnology, Singapore

NOVEMBER 2009 | VOLUME 12 | NUMBER 11

USA Jackie Yi-Ru Ying Institute of Bioengineering and Nanotechnology, Singapore NOVEMBER 2009 | VOLUME 12 |

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www.materialstoday.com

CONTENTS

Contents

Regulars

Editorial 1

Editorial

1

Energy crisis

Can fusion and fission harness a new hope for our energy needs?

Comment | Bruce Mendelsohn 6

Comment | Bruce Mendelsohn

6

Transforming Engineers into Engineering Leaders

A Snapshot of the Bernard M. Gordon-MIT Engineering Leadership Program

Research News 8

Research News

8

Pencilled in: graphite’s ferromagnetism | Magnetricity: The new magnetic electricity | New nano-sensor speeds up DNA detection | Butterfly wings inspire new research | Small and powerful nuclear battery developed | Every silver-lined solar cell | Origami tubes

developed | Every silver-lined solar cell | Origami tubes Opinion | Sanjeev Mukerjee et al. 62

Opinion | Sanjeev Mukerjee et al.

62

The scientific symposium “Materials Challenges for Clean Energy in the New Millennium”

The global energy problem is rapidly intensifying due to escalating competition for resources from emerging, populous countries such as China, India, and Brazil and compelling evidence pointing towards the imperative need for controlling greenhouse gas and carbon emissions.

Updates

for controlling greenhouse gas and carbon emissions. Updates Diary 64 Cover Image Functionalized Dendrimer with SWNT

Diary

64

Cover Image

Functionalized Dendrimer with SWNT for hydrogen storage

Hydrogen has been recognized as an ideal energy carrier and is difficult to store. Since the discovery of carbon nanotubes, SWNTs have been suggested as suitable gas storage because of its few nanometers in diameters size. Pores of molecular dimensions can absorb large quantities of gasses; hydrogen can condense to high density inside the narrow SWNTs. Computational techniques shows that by carefully chosen functionalized Polyamidoamine dendrimer with the critical dimensions of SWNTs have 8.57 weight % storage capacities at room temperature under modestly high pressure. 85% of adsorbed hydrogen can be released under atmospheric pressure and room temperature.

Leela Rakesh, Prof. Stan Hirschi, Mark Kujawski (University of Maryland), Mike Lalko, Pratik Chhetri, Bard Fahlman and Anja Mueller, Central Michigan University.

Bard Fahlman and Anja Mueller, Central Michigan University. 8 Magnetic moments captured in graphitic defects 9
8 Magnetic moments captured in graphitic defects
8 Magnetic moments captured in graphitic defects
9 Butterfly wing replica
9 Butterfly wing replica
10 Typical polymer solar cell material
10 Typical polymer solar cell material

NOVEMBER 2009 | VOLUME 12 | NUMBER 11

graphitic defects 9 Butterfly wing replica 10 Typical polymer solar cell material NOVEMBER 2009 | VOLUME

3

CONTENTS

www.materialstoday.com

CONTENTS www.materialstoday.com Lead story 12 Structural materials for fission & fusion energy In many cases, a

Lead story

12

Structural materials for fission & fusion energy

In many cases, a key strategy for designing high-performance radiation-resistant materials is based on the introduction of a high, uniform density of nanoscale particles that simultaneously provide good high temperature strength and neutron radiation damage resistance.

Steven J. Zinkle and Jeremy T. Busby

Energy uncovered

Steven J. Zinkle and Jeremy T. Busby Energy uncovered Review 20 Discovery and design of nuclear
Steven J. Zinkle and Jeremy T. Busby Energy uncovered Review 20 Discovery and design of nuclear
Steven J. Zinkle and Jeremy T. Busby Energy uncovered Review 20 Discovery and design of nuclear
Steven J. Zinkle and Jeremy T. Busby Energy uncovered Review 20 Discovery and design of nuclear

Review

20

Discovery and design of nuclear fuels

Multi-scale models and simulations are used to predict irradiation effects on properties such as thermal conductivity, oxygen diffusivity, and thermal expansion.

Marius Stan

oxygen diffusivity, and thermal expansion. Marius Stan Review 30 Nuclear reactor materials at the atomic scale

Review

30

Nuclear reactor materials at the atomic scale

With the renewed interest in nuclear energy, developing new materials able to respond to the requirements of the next- generation fission and future fusion reactors becomes a priority.

Emmanuelle A. Marquis, Jonathan M. Hyde, David W. Saxey, Sergio Lozano-Perez, Vanessa de Castro, Daniel Hudson, Ceri A. Williams, Samuel Humphry-Baker and George D.W. Smith

Ceri A. Williams, Samuel Humphry-Baker and George D.W. Smith Review 38 Modeling plasma facing materials for

Review

38

Modeling plasma facing materials for fusion power

Duffy describes the methods used for modeling the response of plasma facing materials to the conditions experienced in a fusion reactor.

D. M. Duffy Review 46 Multiscale Modelling: the role of helium in iron This review
D. M. Duffy
Review
46
Multiscale Modelling: the role of helium in iron
This review discusses the modelling paradigms used to investigate
and obtain an understanding of the mechanisms at play in helium
bubble nucleation and growth in ferritic steels.
Maria Samaras
Review
54
Neutron scattering and hydrogen storage
Hydrogen has the largest scattering interaction with neutrons of
all the elements in the periodic table making neutron scattering
ideal for studying hydrogen storage materials.
A. J. Ramirez-Cuesta, M. O. Jones and W. I. F. David
4
NOVEMBER 2009 | VOLUME 12 | NUMBER 11

Next issue

Materials Today will feature the current state of play in the fascinating world of metamaterials, current research trends, applications and future direction.

Optical nano-

antennas and

metamaterials

A review of some of the recent

approaches to transmission enhancement and light harvesting.

Anisotropic

metalmaterial

devices

Recent progress on the parametric design of transformation devices

is covered in this review article.

Phononic crystals and acoustic metamaterials

Current research and trends in phononic crystals are covered in this paper.

Electromagnetic wave in 2D photonic crystals

Progress on the negative refraction and the abnormal transmission of electromagnetic waves in 2D photonic crystals is covered in this paper

Resonance

properties of

metallic ring

systems

A rigorous mode-expansion

theory is proposed to help

understand resonance properties

of metallic ring systems.

Mie resonance- based dielectric metamaterials

Novel applications are discussed in this paper

BUDDY D. RATNER 2009 Gold Medal 2009 Acta Materialia, Inc. is pleased to announce that
BUDDY D. RATNER 2009 Gold Medal 2009 Acta Materialia, Inc. is pleased to announce that
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Gold Medal 2009

Acta Materialia, Inc. is pleased to announce that the recipient of the 2009 Acta Biomaterialia Gold Medal Award is Dr. Buddy D. Ratner, Professor of Bioengineering and Chemical Engineering at the University of Washington. The Award recognizes excellence in the research and the practice of biomaterials.

Professor Ratner’s seminal explorations of biosurfaces and biomaterials/tissue interactions as applied to tissue engineering, understanding biocompatibility and developing medical products have profoundly contributed to the advancement of biomedical science and technology. His record of over 400 scholarly works, over 18 issued patents and extensive leadership in education, academic and professional service has resulted in many awards and honors over his distinguished forty year career.

Professor Ratner formally received his award at the 2009 meeting of the European Society for Biomaterials in Lausanne, Switzerland, on September 11, and presented a plenary talk entitled: Biocompatibility Vitalized:

The Paradigm Shifts in Healing and Regeneration.

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COMMENT

Transforming Engineers into Engineering Leaders

6

COMMENT Transforming Engineers into Engineering Leaders 6 A Snapshot of the Bernard M. Gordon-MIT Engineering Leadership

A Snapshot of the Bernard M. Gordon-MIT Engineering Leadership Program

Bruce Mendelsohn | Massachusetts Institute of Technology, USA | brucem@MIT.EDU

In its recent report The Engineer of 2020: Visions of Engineering in the New Century, the U.S.-based National Academy of Engineering outlined the various fields in which students educated in engineering might go on to be leaders, including research, product and system development, business and even broader professions. The NAE concludes that:

“In preparation for this opportunity, engineers must understand the principles of leadership and be able to practice them in growing proportions as their careers advance. Complementary to the necessity for strong leadership ability is the need to also possess a working framework upon which high ethical standards and a strong sense of professionalism can be developed.”

Echoing that sentiment, in Spring 2006, a Massachusetts Institute of Technology Task Force on the Undergraduate Educational Commons stated:

“A MIT education should be designed to encourage students to assume leadership roles in a global society.”

MIT’s existing academic engineering programs provide a firm basis of disciplinary knowledge and the modes of thought critical to the particular field—principally problem solving and research for engineers; and courses in the humanities and social sciences offer other disciplines with new ways of thinking and experiencing the world.

We acknowledge, however, that while MIT produces some of the best-educated engineers in the world, many of our graduates do not possess strong leadership skills. We further acknowledge that we could do a better job of preparing our students in the broader array of personal and professional capabilities from which they will draw in life:

The Bernard M. Gordon-MIT Engineering Leadership Program responds to the calls of the engineering profession and seeks to fill the gaps in the traditional

MIT education, helping to prepare our engineering undergraduate students for the leadership roles in life.

“In the Gordon-MIT Engineering Leadership Program, students develop their integrity, discipline and a stronger character and an understanding of other human beings,” says Program Benefactor Bernard M. Gordon (MIT ’48, M.S. ’49), whose Bernard M. Gordon Foundation donated $20 million to start the program. “These essential leadership qualities — along with their technical ability — will help them prepare for the real-life situations they’ll confront in the competitive technical world.”

Housed in MIT’s School of Engineering, the Gordon ELP aim is to transform today’s engineering undergraduates into tomorrow’s engineering leaders. The program strives to do so through a unique combination of project-based learning, extensive interaction with industry leaders, hands-on product development, engineering leadership labs, and authentic leadership challenges and exercises.

The program’s educational objective is therefore to provide opportunities for all engineering students to further develop, deepen, and broaden their engineering leadership attitudes and skills.

In specially designed “short courses”, students accepted into the Gordon-MIT ELP are exposed to relevant frameworks, models, and cases. A select group of approximately 30 “Gordon Engineering Leaders” apply and practice the approaches gleaned through that exposure in weekly “Engineering Leadership Labs” (ELLs). Guided learning activities in the ELLs include role-plays, simulations, design-implement activities, and analyses of case studies, films, and books related to engineering leadership.

The program’s engineering leadership lessons are delivered through an alliance of program faculty and staff, MIT departments, related MIT programs, MIT

alumni, concerned industry representatives, all of whom interact synergistically with undergraduates.

Both at the introductory (freshman and sophomore) and advanced (junior and senior) levels, the Gordon- MIT ELP enhances current hands-on, project-based courses and inspires the design and development of new and authentic project-based courses throughout MIT’s engineering disciplines.

“To my knowledge, this program is unique in what it’s offering,” says Dr. Ruth Graham, whom the program commissioned to conduct a benchmarking study of engineering leadership education programs worldwide (see Materials Today, September 2008).

“Most programs I highlight in the report are extra- curricular and cater to only a small proportion of the engineering cohort. In contrast, the Gordon-MIT ELP is offered to all MIT engineering students and provides a range of curricular and extra-curricular experiences. It also has an aggressive external distribution objective, which will provide much needed support and information to other engineering schools interested in developing the leadership abilities of their students.” Finally, she adds, “Through the Gordon-MIT ELP, MIT is developing a model that others can learn from, and that will potentially contribute to developing the next generation of engineering leaders.”

“What’s important in engineering education? Making universities and engineering schools exciting, creative, adventurous, rigorous, demanding and empowering environments is more important than specifying curricular details,” says Dr. Charles Vest, NAE President and former President of MIT. “The Gordon-MIT Engineering Leadership Program is an example of how MIT is working to empower today’s engineering undergraduates with critical leadership skills that will help them to become tomorrow’s engineering leaders.”

For more information, visit http://web.mit.edu/gordenelp/.

engineering leaders.” For more information, visit http://web.mit.edu/gordenelp/. NOVEMBER 2009 | VOLUME 12 | NUMBER 11

NOVEMBER 2009 | VOLUME 12 | NUMBER 11

In partnership with In-Situ Nanomechanical Testing Techniques: Opening Doors to a New World of Materials
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RESEARCH NEWS

Pencilled in: graphite’s ferromagnetism

MAGNETISM

Graphite should not be ferromagnetic because it has none of the high-level 3d and 4f electrons seen in iron that can align to produce a magnetic field. Graphite contains only sp electrons, which produce only weak magnetic signals. However, researchers in The Netherlands [Flipse et al., Nature Phys. (2009) DOI:

10.1038/NPHYS1399] have now obtained direct evidence for ferromagnetism in pyrolytic graphite. Their discovery could have applications in sensor technology and ultimately, spintronics. The idea that graphite might display permanent magnetism, or ferromagnetism, has remained controversial for at least a decade. Although several independent teams have hinted at the possibility through their experiments, it is well known that graphite possesses only weakly magnetic sp electrons and its Curie point is above room temperature so ferromagnetism seemed to be precluded from its repertoire of properties. The earlier research hinted, however, that imperfections in the graphite crystal lattice might underpin any demonstration of ferromagnetism. Researchers at Eindhoven University of Technology and Radboud University of Nijmegen point out that besides the experiments with

of Nijmegen point out that besides the experiments with Magnetic moments captured in graphitic defects. graphite,

Magnetic moments captured in graphitic defects.

graphite, some degree of ferromagnetism has also been demonstrated in polymerized fullerenes, carbon nano foams, and proton- irradiated thin carbon films as well as nanoscopic diamonds implanted with nitrogen and carbon ions. These experiments imply that carbon could display inherent ferromagnetic behaviour despite the controversy. The team has studied a particular form of carbon, highly oriented pyrolytic graphite (HOPG), using bulk magnetization

measurements at room temperature in conjunction with magnetic force microscopy (MFM). The MFM tip itself is magnetized in two opposite directions and so disturbances caused by it being in close proximity to another magnetic material can be detected. The researchers have now uncovered ferromagnetic order at the points where defect structures are present in the HOPG. The ferromagnetism arises solely because of the way the electrons become arranged at the boundaries between crystal grains, they say. Two-dimensional arrays of point defects between individual carbon sheets become magnetically coupled giving rise to the permanent magnetic behaviour of the bulk graphite. They emphasise that they also have evidence to show that the ferromagnetism is not due to magnetic impurities in the HOPG. The team’s theoretical analysis of the system

corroborates their experimental results, offering

a value for the magnetic measurements close

to that seen in the experiments. The results end

a decade or more of debate about graphite’s

magnetic properties and could open up ferromagnetic graphite for use in biosensors and spintronics. David Bradley

8

Magnetricity: The new magnetic electricity

MAGNETISM

A magnetic charge can behave and interact just

like an electric charge in some materials, according

to new research led by the London Centre for

Nanotechnology which could lead to a reassessment

of current magnetism theories, as well as significant

technological advances. The research, published today in Nature [Bramwell et al., Nature (2009) 461] proves the existence of atom- sized magnetic charges called ‘magnetic monopoles’

that behave and interact just like more familiar electric charges. It also demonstrates a perfect symmetry between electricity and magnetism – a phenomenon dubbed ‘magnetricity’ by the authors from the London Centre for Nanotechnology and STFC’s ISIS Neutron and Muon Source .

In order to prove experimentally the existence of

magnetic current for the first time, the team mapped

Onsager’s 1934 theory of the movement of ions in water onto magnetic currents in a material called spin ice. They then tested the theory by applying a magnetic field to a spin ice sample at a very low temperature and observing the process using muon relaxation at ISIS, a technique which acts as a super microscope allowing researchers to understand the world around us at the atomic level. The experiment allowed the team to detect magnetic charges in the spin ice (Dy2Ti2O7), to measure their currents, and to determine the elementary unit of the magnetic charge in the material. The monopoles they observed arise as disturbances of the magnetic state of the spin ice, and can exist only inside the material. Professor Steve Bramwell, LCN co-author of the paper, said: “Magnetic monopoles were first predicted to exist in 1931, but despite many searches, they have

to exist in 1931, but despite many searches, they have NOVEMBER 2009 | VOLUME 12 |

NOVEMBER 2009 | VOLUME 12 | NUMBER 11

never yet been observed as freely roaming elementary particles. These monopoles do at least exist within the spin ice sample, but not outside. “It is not often in the field of physics you get the chance to ask ‘How do you measure something?’ and then go on to prove a theory unequivocally. This is a very important step to establish that magnetic charge can flow like electric charge. It is in the early stages, but who knows what the applications of magnetricity could be in 100 years time.” Dr Sean Giblin, instrument scientist at ISIS and co-author of the paper, added: “The results were astounding, using muons at ISIS we are finally able to confirm that magnetic charge really is conducted through certain materials at certain temperatures – just like the way ions conduct electricity in water.”

Jonathan Agbenyega

RESEARCH NEWS

New nano-sensor speeds up DNA detection

BIOMATERIALS

A team of scientists at Singapore’s Institute of Bioengineering and Nanotechnology (IBN) has developed a novel ultra-sensitive electronic biosensor for DNA testing that offers a faster, more accurate and cost-efficient alternative to the conventional methods involving the use of the polymerase chain reaction. First laboratory tests obtained by the IBN scientific team, led by Dr. Zhiqiang Gao, were published in last September’s issue of the Journal of the American Chemical Society [Roy et al., doi:10.1021/JA901704T]. The high performance of the new sensor, called the “Nanogap Sensor Array”, comes in part from its unique design which consists of a vertically aligned nanostructure and a two-surface configuration based on electronic transduction. The sensor includes a pair of micro-sized metal electrodes separated by a so-called “nanogap” (5-20 nm). Another feature of the sensor is its ability to capture DNA strands in a very unique manner by “sandwiching” them between the two surfaces of the sensor. Those surfaces are coated with a chemically treated “capture probe”

are coated with a chemically treated “capture probe” Schematic illustration of IBN’s Nanogap Sensor Array

Schematic illustration of IBN’s Nanogap Sensor Array (photo credit: IBN).

solution exclusively developed by the IBN. This treatment facilitates the capture and adherence of the DNA strands to the surface, thus resulting in a faster and more accurate analysis. The new biosensor, which translates the presence of DNA into a measurable electric signal, has shown an excellent sensitivity in first experimental results. Not only it is capable of detecting trace amounts of DNA as efficiently as conventional DNA biosensors, but its unique

sensor offers “a scalable and viable alternative for DNA testing” and “holds significant promise for the detection and diagnosis for debilitating diseases such as cancer, cardiovascular problems and infectious viruses”. The Institute of Bioengineering and Nanotechnology (IBN) was established in 2003, as a National Research Institute under the Agency for Science, Technology and Research, Singapore. More information on the Institute is available at:

features make it very suitable for cost-effective

www.ibn.a-star.edu.sg

mass production. According to Dr. Gao, the new

Elisabeth Lutanie

Butterfly wings inspire new research

BIOMATERIALS

A technique that enables replicas of biological structures, such as butterfly wings, to be made on a nanometric scale has been developed by a team of researchers from the State University of Pennsylvania and the Universidad Autónoma de Madrid in Spain. The study, published in Bioinspiration & Biomimetics (doi: 10.1088/1748-3182/4/3/034001), could have many applications, such as in optical diffusers and coverings that maximize solar cell light absorption, as well as in fabrics, textiles and surfaces based on the nanoscale photonic structures responsible for the vibrant colors in many butterfly wings. It could also be possible to have swatches of fabrics that would sense such things as magnetic fields and temperature changes. Insects’ colours and their ability to change colours depending on the angle, or their ability to appear metallic, are determined by tiny nano-sized photonic structures that can be found in their cuticle. The research has focused on these biostructures to develop devices with light-emitting properties. The team of Akhlesh Lakhtakia, Raúl Martín-Palma, Michael Motyka and Carlo Pantano, studied successful natural systems with the aim of deriving the essential design elements, and hence improve man-made systems.

design elements, and hence improve man-made systems. Butterfly wing replica. As Lakhtakia points out, there is

Butterfly wing replica.

As Lakhtakia points out, there is the possibility of “replicating highly convoluted surfaces down to the smallest feature size, thereby reproducing some of their most desired optical, electronic, mechanical and chemical functionalities.” Up to now, the few methods that can be used to replicate biostructures on a nanometric scale often damage the original biostructure, because they are used in corrosive atmospheres or at high temperatures. This new technique overcomes these

problems, as it is employed at room temperature and does not require the use of toxic substances. In order to create new biomaterial, the team employed a technique called conformal-evaporated-film-by- rotation (CEFR), which combines thermal evaporation and substrate rotation in a low-pressure chamber to replicate the surface, and used immersion in an aqueous orthophosphoric acid solution to dissolve the chitin. As well as butterfly wings, the compound eyes of insects such as flies, bees and wasps are also possible sources for a range of new applications, including miniature cameras and optical sensors installed in cars, mobile telephones and displays. There is also potential for use in surgical procedures and the security industry. The scientists are confident that the technique can also be used to replicate other biological structures, such as beetle shells. The researchers admit that only bio-replication that could be scaled up and not deplete natural populations of the species whose surfaces are being replicated is going to be industrially viable, humane and ethical. However, they are confident that they can achieve this through the further study of biostructures.

Laurie Donaldson

NOVEMBER 2009 | VOLUME 12 | NUMBER 11

they can achieve this through the further study of biostructures. Laurie Donaldson NOVEMBER 2009 | VOLUME

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RESEARCH NEWS

Small and powerful nuclear battery developed

ENERGY

A team of researchers have built a very small

and efficient nuclear battery, which is intended to power various micro/nanoelectromechanical

systems. The radioisotope battery is tiny – the current model is about the size and thickness of a penny – and innovatively uses a liquid semiconductor rather than the usual solid one.

One of the main problems up to now has been that these systems need power to function, and the battery for such a device can be much larger and heavier than the device itself. The ambition for the research team has been to develop an energy source that is both small and light, and produces more power for a longer time. Another barrier to overcome was that the use

of a radioactive battery normally means, when

you harvest the energy, that part of the radiation

energy can damage the lattice structure of the

solid semiconductor; however, by operating with

a liquid semiconductor, that problem can be

minimized. The team, from the University of Missouri,

whose research has previously been published

in the Journal of Applied Physics Letters

[doi:10.1063/1.3160542] and Journal of

Radioanalytical and Nuclear Chemistry [doi:

10.1007/s10967-009-0157-9], have therefore developed a nuclear energy source that is smaller, lighter and more efficient than previously created, based at the university’s research reactor. Microscale devices, smaller than a computer chip, are already used to deploy airbags, sense tire pressure, work in jet printers, measure biological contaminants, and perform scientific tests. But there is a great need for systems that contain more power and last longer, which is why the radioisotope battery has been created, as a means of producing power with a high energy density. The device that the team is working on can provide power density six orders of magnitude higher than chemical batteries. The researchers are quick to allay concerns over safety, arguing that nuclear power sources are already powering a variety of devices, such as pace-makers, space satellites and underwater systems. In addition, andmentioning that due to the advanced sealing and packaging technologies with lower shielding required materials, the nuclear power source will safely power without

the nuclear power source will safely power without Fuel cell. any of the problems that the

Fuel cell.

any of the problems that the public associates with nuclear energy. As Dr. Jae Kwon points out, the research “has shown a new path for the nuclear battery research”, and it is expected thats further promising results will follow. The team will now move on to developing and improving its efficiency and higher output power, as well as decreasing its size (perhaps, one day, to the width of a human hair), as well as testing various other materials. Although there is a long way to go before the battery is ready for commercial marketing, such an efficient and long-lived power source would be a popular one in the industry. Laurie Donaldson

10

Every silver-lined solar cell

ENERGY

The future of lighter, cheaper, and more-flexible solar cells looks bright thanks to US research into silver nanoparticles. Scientists at Ohio State University have added the nanoparticles to their polymer semiconductor photovoltaic materials and observed a relative efficiency boost of 12 percent. The discovery could pave the way to flexible organic photovoltaics with all the advantages of ease of manufacture and inexpensive starting materials. To prepare their modified organic photovoltaic materials, the team created a colloidal solution of silver nanoparticles. Organic capping groups stabilize the nanoparticles and prevent them from sticking together, Transmission electron microscopy reveals that the particles are highly uniform in size, with an average diameter of about 4 nanometres, and align into a regular mosaic with controlled spacing between them, which could be key to light absorption. The team then applied this colloidal preparation to their organic bulk heterojunction photovoltaic devices, which are constructed from a polythiophene- fullerene material on an indium-tin oxide/glass substrate.

fullerene material on an indium-tin oxide/glass substrate. Typical polymer solar cell material (right) and one

Typical polymer solar cell material (right) and one containing silver nanoparticles (left). (Photo by Jo McCulty, courtesy of Ohio State University).

Paul Berger of Ohio State University and his team report [Berger et al., Solar Energy Mater Solar Cells, (2010) in press] that they get 70 amps per square metre with the silver nanoparticles but only 62 amps without the additive. Their initial tests revealed that the nanolayer boosts optical absorption and photocurrent for the photovoltaic devices. This occurs because an increased electric field is induced in the photoactive layer by the excited localized surface plasmons of the silver nanoparticles. In other words, the nanotechnology essentially amplifies the signal

words, the nanotechnology essentially amplifies the signal NOVEMBER 2009 | VOLUME 12 | NUMBER 11 by

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by absorbing solar energy from a wider range of wavelengths. Previous researchers have attempted to use capped silver nanoparticles to boost solar energy conversion efficiencies. However, those experiments were inconsistent, producing a broad range of nanoparticles sizes and so did not achieve the efficiency boost that Berger and his team have now observed. Berger explains that implications of this development:

“The light absorption of polymer solar cells is inadequate today,” he says, “The top-performing materials have an overall efficiency of about 5 percent. Even with the relatively low production cost of polymers compared to other solar cell materials, you’d still have to boost that efficiency to at least 10 percent to turn a profit.” “By changing the organic coating, we could change the spacing of the particles and alter the size of each particle,” adds Berger, “By fine-tuning the mosaic pattern, we could move the enhanced absorption to different wavelengths, and thus get even more of an improvement. I think we can get several percent more.”

David Bradley

Origami tubes

NANOTECHNOLOGY

A new approach to nanoelectronics could see

researchers using DNA origami to self-assemble circuits from carbon nanotubes and other materials.

In 2006, Caltech scientist Paul Rothemund

invented a DNA origami technique to make different structures on the nano scale. The technique exploits the well-known self-assembly properties of single-stranded DNA to make

almost limitless shapes and patterns that can be programmed by synthesising appropriate DNA sequences. Amusingly, Rothemund produced nanoscopic smiley faces, snow flakes and even a map of the Americas. Hareem Maune, at the time a graduate student

in applied physics working under Marc Bockrath

on carbon nanotubes, Si-ping Han, a material

science graduate student working for

William Goddard III, and then undergraduate Robert Barish, working with Erik Winfree, reasoned that DNA origami might provide

a neat way to construct nanoscale devices.

[Maune et al., Nature Nanotech. (2009) 10.1038/

nnano.2009.311]

Fundamentally, the researchers figured that DNA origami could be used to make two-dimensional “breadboards”, the patterned base layer for building a circuit from components, in this case

carbon nanotubes. Sophisticated devices might be built by attaching the components to a template pattern on a breadboard assembled with the right DNA sequences. “For nanoscale devices to become commercially useful,” says Goddard, “it is essential to have

a technology that is scalable, that is, allows

thousands, millions, billions to be manufactured simultaneously.” Until now, attempts at making nanoscale devices incorporating multiple carbon nanotubes have been hampered by the difficulty

RESEARCH NEWS

(a)

(b)

DNA origami

(c)
(c)

in placing the nanotubes into the correct geometry in a scalable way. One challenge is to provide molecular attachment points on the featureless carbon nanotube surface that could both anchor the nanotube and identify different nanotubes. “This difficulty with chemically grabbing a nanotube at a well-defined ‘handle’ is the essence of the problem when you’re trying to place nanotubes where you want them,” Winfree explains. DNA could provide the needed hook. “DNA is the perfect molecule for recognizing other strands of DNA, and single-stranded DNA also just happens to like sticking to carbon nanotubes,” explains Han, “so we mix bare nanotubes with DNA molecules in salt water, and they stick all over the nanotubes’ surfaces. However, we make sure that a little bit of each DNA molecule is protected, so that that little portion doesn’t stick to the nanotube, and we can use it to recognize the DNA attached to the DNA origami instead.” By creating DNA-coated nanotubes with two different labelling sequences, the team gave

the nanotubes the ability to sit on one of two different positions demarcated by complementary DNA sequences on their breadboard. Thus, they can essentially “paint” a device pattern in two colours. “A standard DNA origami is a rectangle about 100 nm in size, with over 200 ‘pixel’ positions where arbitrary DNA strands can be attached,” Winfree says. By “painting” a stripe of one DNA sequence perpendicular to the other, they were able to get the carbon nanotubes to attach and form perpendicular crosses, resulting in field-effect transistors (FET), one of the most basic devices for building semiconductor circuits. Indeed this approach can be extended to many different colours to enable the assembly of complex devices. Although there are challenging problems to overcome, the approach is, in principle, highly scalable. A DNA origami template could one day be used to self-assemble complex logic units, and to do this for billions or trillions of units that self- assemble in parallel, the researchers point out. David Bradley

Erratum

Materials Today (2009) 12 (10), 22-32. “Revolutionizing Biodegradable Metals” by Yun et al.

Add references 113 to 118 to make the literature survey more current.

113. Witte, F., et al., Biomaterials, (2006), 27, 1013.

114. Witte, F., et al., Current Opinion in Solid State & Materials Science, (2008) 12, 63.

115. Witte, F., et al., Acta Biomaterialia (2009) DOI: 10.1016/j.actbio.2009.10.012.

116. Hermawan, H., et al., Acta Biomaterialia (2009) DOI: 10.1016/j.actbio.2009.10.006.

117. Hänzi, A.C., et al., Acta Biomaterialia (2009) DOI: 10.1016/j.actbio.2009.10.008.

118. Hort, N., et al., Acta Biomaterialia (2009) DOI: 10.1016/j.actbio.2009.09.010.

Corrections to the text. On page 23, 4 th sentence from the bottom of column 2, “crystalline” should be replaced with “thin”. On page 24, 5 th line down first column, reference 5 should follow “Song et al”. On page 29, 8 th sentence from the bottom of column 2, reference 76 should be 83. On page 30, the correct citation in the caption of Fig. 9 is 113, not 91. On page 30, 4 th sentence from the bottom of column 1, replace citation 80-91 with 76-79.

Please add to the acknowledgment: The Mg Y 4% alloy material used in experiments described in this article was provided by Dr.-Ing. Norbert Hort of the GKSS- Forschungszentrum Geesthacht GmbH, MagIC – Magnesium Innovation Center, Head Magnesium Processing Group, Max-Planck-Str. 1, Geb. 47, D-21502 Geesthacht, Germany.

NOVEMBER 2009 | VOLUME 12 | NUMBER 11

Processing Group, Max-Planck-Str. 1, Geb. 47, D-21502 Geesthacht, Germany. NOVEMBER 2009 | VOLUME 12 | NUMBER

11

Structural materials for fission & fusion energy

Structural materials represent the key for containment of nuclear fuel and fission products as well as reliable and thermodynamically efficient production of electrical energy from nuclear reactors. Similarly, high- performance structural materials will be critical for the future success of proposed fusion energy reactors, which will subject the structures to unprecedented fluxes of high-energy neutrons along with intense thermomechanical stresses. Advanced materials can enable improved reactor performance via increased safety margins and design flexibility, in particular by providing increased strength, thermal creep resistance and superior corrosion and neutron radiation damage resistance. In many cases, a key strategy for designing high-performance radiation- resistant materials is based on the introduction of a high, uniform density of nanoscale particles that simultaneously provide good high temperature strength and neutron radiation damage resistance.

Steven J. Zinkle* and Jeremy T. Busby Materials Science and Technology Division, Oak Ridge National Laboratory, P.O. Box 2008, Oak Ridge, Tennessee, 37831-6132 USA *Email: zinklesj@ornl.gov

A diverse portfolio of energy options (encompassing renewable energy, biofuels, nuclear power, and fossil energy systems with improved thermodynamic efficiency and improved control of effluents), coupled with improvements in energy efficiency for buildings, transportation and industry, is an attractive strategy to achieve cost-effective and environmentally sustainable energy resources that will enable improvements in the worldwide standard of living. Sustained improvements in the operating performance of fission reactors 1,2 , along with advances in the plasma physics knowledge required for heating and controlling

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physics knowledge required for heating and controlling 12 NOVEMBER 2009 | VOLUME 12 | NUMBER 11

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fusion energy reactions 3-5 , suggest that fission and fusion energy can be important components of the overall energy portfolio for the 21st century and beyond.

Fission: an increasingly reliable supplier of baseload electricity.

Currently, over 430 nuclear fission reactors in 30 countries provide about 15% of the world’s supply of electricity 6 . The vast majority of these reactors are based on uranium dioxide fuel pellets arranged in long cylinders (“fuel rods”) with surrounding flowing water channels.

ISSN:1369 7021 © Elsevier Ltd 2009

Structural materials for fission & fusion energy

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A typical power reactor core contains about 50 000 fuel rods with a height of ~4 m and diameter ~1 cm. Since the 1980s, fuel burnup and cycle length for nuclear reactors have steadily increased due to improvements in water chemistry control and development of improved corrosion-resistant steam generator and fuel cladding structural materials, and are the primary reasons that the average capacity factor for U.S. fission reactors is now >90 % (compared to ~74 % for coal fired power plants) 7 . As illustrated in Fig. 1, a diverse range of structural materials are used for a wide variety of important roles in fission reactors 8 . The fuel cladding serves to reliably contain the fuel and radioactive fission products while simultaneously efficiently transferring the intense nuclear heat from the fuel to the coolant. The typical heat flux through the cladding is ~1 MW/m 2 (~1% of the heat flux at the surface of the sun). Zirconium alloys are used as fuel cladding in most commercial reactors, due to their compatibility with UO 2 and water, their adequate thermal conductivity and ease of manufacturing. Wire wrap is used to prevent constriction of coolant channels from slight fuel pin bowing. The fuel typically remains in the reactor for several years, with the cladding continuously exposed to high temperature (~300 °C), mechanical stress, and intense radiation. Key concerns include oxidation, hydriding, build-up of low thermal conductivity

corrosion deposits, and effect of hydrogen on cracking and corrosion. The ~100 tonne reactor core is secured in place by a variety of fuel rod constraint and reactor core support components typically constructed of austenitic stainless steel and some Ni-base alloys such as X-750. These core internal structures must reliably operate for over 30 years in a high radiation environment (resulting in higher accumulated doses than the fuel cladding in many cases) at ~300 °C without substantial dimensional changes or degradation in mechanical properties due to stress corrosion cracking or radiation damage. The reactor pressure vessel (quenched and tempered Mn-Mo-Ni low-alloy pressure vessel steel) serves as the critical safety boundary between the reactor and the environment, and is generally considered the key lifetime-limiting (irreplaceable) component for a nuclear reactor. A key concern is loss of fracture toughness due to radiation-induced defect cluster hardening and radiation-induced precipitation. The embrittlement is monitored by regular mechanical property testing of surveillance coupon specimens located at the inside wall of the pressure vessel. Piping and heat exchanger materials (ferritic steels and Ni-base alloys such as Alloy 600 and 690) are designed to enable reliable and thermodynamically efficient conversion of thermal energy from the reactor into steam that drives turbines to generate electricity. Due to the desire for reliable operation for decades at elevated temperatures in an aqueous

operation for decades at elevated temperatures in an aqueous Fig. 1 Schematic of key components utilizing

Fig. 1 Schematic of key components utilizing structural materials in pressurized water fission reactor 8 .

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utilizing structural materials in pressurized water fission reactor 8 . NOVEMBER 2009 | VOLUME 12 |

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Structural materials for fission & fusion energy

environment at 300 to 350 ºC, key concerns for the piping and heat exchanger materials include thermal aging and complex water chemistry issues that may induce corrosion or stress corrosion cracking. Aqueous corrosion is a complex form of degradation that is dependent on temperature, material condition, material composition, water purity, water pH, water impurities, and dissolved gas concentrations. The predominant corrosion mechanism varies with location in the reactor core and multiple mechanisms may be simultaneously operating 9,10 . These include the mechanisms of uniform corrosion, boric acid corrosion, flow accelerated corrosion, and/or erosion corrosion which will occur over a large area in a fairly homogenous manner. Localized corrosion modes occur over much smaller areas, but at much higher rates than general corrosion and include crevice corrosion, pitting, galvanic corrosion, and microbiologically influenced corrosion. Finally, environmentally assisted cracking includes other forms of degradation, which are closely related to localized or general corrosion with the added contribution of stress. In a light water reactor, a number of different environmentally assisted cracking mechanisms are observed: intergranular stress-corrosion cracking 11 , transgranular stress corrosion cracking, primary water stress corrosion cracking, irradiation-assisted stress corrosion cracking (IASCC) and low-temperature crack propagation. While all forms of corrosion are important in managing a nuclear reactor, IASCC has received particular attention over the last four decades due both to its severity and unpredictability 12 . Despite over thirty years of international study, the underlying mechanism of IASCC is still unknown, although recent work led by groups such as the Cooperative IASCC Research Group has identified several possible causes.

Fusion: a potentially attractive but technologically challenging endeavor.

Sustained progress over several decades has taken fusion researchers to the brink of demonstrating the plasma physics feasibility of fusion energy via magnetically-confined 4,13,14 and inertially-confined 13,15,16 concepts. Major fusion facilities recently completed (e.g., National Ignition Facility) 17 or under construction (e.g., ITER) 18 are designed to explore the key remaining plasma physics issues near reactor-relevant operating conditions. If successful, the focus of attention will shift towards large-scale next-step fusion facilities that will examine the daunting technological hurdles to practical fusion energy. A schematic of a prototypic magnetic fusion energy reactor 5 is shown in Fig. 2. The fusion reactions are induced within a toroidal- shaped high temperature ionized plasma that is shaped by powerful toroidal and poloidal field magnets. The heat and energetic neutrons produced by the deuterium-tritium (D-T) fusion reaction are absorbed by the surrounding first wall, blanket, and divertor components. The fusion reaction occurs inside a vacuum vessel to prevent atmospheric contamination of the D-T plasma. The major functions of the blanket region are to efficiently capture the energy produced by the fusion

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by the fusion 14 NOVEMBER 2009 | VOLUME 12 | NUMBER 11 Fig. 2 Schematic of

Fig. 2 Schematic of key components in a magnetically-confined fusion reactor, based on the ARIES-AT tokamak reactor design study 5 .

reactions and transfer the heat to a coolant for electricity generation, and to create and extract fresh tritium fuel (by utilizing nuclear transmutation reactions with lithium-containing liquid or solid materials) to enable continuous operation of the fusion energy system. A wide variety of structural materials, reactor coolants, and tritium generation materials systems have been evaluated for potential use in future fusion reactors. Table 1 summarizes the material combinations that are considered to be the most promising based on thermodynamic efficiency, neutronics, chemical compatibility, and other engineering considerations 19,20 . High-performance structural materials will be critical for the future success of proposed fusion energy reactors, which will subject the structures to unprecedented fluxes of high-energy neutrons along with intense thermomechanical stresses and high temperature coolants that may induce corrosion 19,21-31 . Steady-state heat fluxes for first-wall and divertor components in proposed magnetically-confined fusion energy reactors are projected to be in the range of 1 to 10 MW/m 2 , which is substantially higher than the highest heat flux for structural materials in fission reactors (~1 MW/m 2 for the fuel cladding). The

Table 1. Summary of leading proposed structural materials, coolant and tritium generation concepts for fusion energy systems 19,20 . The filled cells in the table indicate material combinations that are under consideration for fusion energy blankets. FLiBe is a LiF- BeF 2 molten salt.

Structural

Coolant/Tritium Generating Material System

Material

Li/Li

He/PbLi

H

2 O/

He/Li

H

2 O/Li

FLiBe/

PbLi

ceramic

ceramic

FLiBe

Ferritic steel

           

V alloy

           

SiC/SiC

           

Structural materials for fission & fusion energy

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design lifetime doses for the first wall and blanket structural materials are about five times higher than the core internal structures for existing fission reactors. In addition, the high average neutron energy associated with the deuterium-tritium fusion reaction compared to fission tends to produce much higher levels of transmutant solutes such as H and He in the structural materials that generally magnify radiation-induced degradation processes. A key additional constraint for fusion structural materials is the international mandate for intrinsic safety (i.e., no public evacuation in case of a loss of coolant accident) and minimal long-term environmental impact (i.e., no long-lived radioisotopes that would require deep geologic burial or equivalent sequestration) for the fusion reactor structures 21,23,26,29,32-35 . Consideration of this reduced- activation mandate, along with the requirement for high performance, leads to three major options for fusion structural materials 21 . Ferritic/ martensitic steel (where high activation solutes such as Mo and Nb in commercial steels are replaced by W and V) is the most mature option 21,36-41 , with natural leveraging of the extensive worldwide expertise and industrial infrastructure in steelmaking. Oxide dispersion strengthened steel represents a potential future higher-performance option if key issues such as property nonuniformity, joining, and high cost can be resolved 39,40,42-46 . Refractory alloys based on either vanadium 47-50 or tungsten 30,51-53 alloys represent a higher performance, higher risk option. Vanadium alloys are particular attractive for self-cooled lithium blanket systems 19 , but are not considered to be viable for other blanket concepts 21 . SiC/SiC ceramic composites offer the potential for the highest thermodynamic efficiency and best safety and waste disposal margins, but are the least developed materials system for large-scale structural applications 21 . Numerous issues including structural engineering design rules, how to achieve leak-tight boundaries for gas cooled systems, joining and other fabrication issues, radiation stability uncertainties, improvement of thermal conductivity (and minimization of radiation- induced degradation), and fabrication cost need further research and development to enable this materials system to achieve its full potential 54-57 .

Radiation damage: A multi-faceted challenge to structural materials in fission and fusion reactors

The energetic neutrons produced by the fission and fusion reactions have sufficient kinetic energy to dislodge substantial numbers of atoms in structural materials from their lattice sites over the projected operating lifetimes of the reactors, creating defects associated with the missing lattice atoms (vacancies) and the dislodged atoms that reside in the lattice interstices (self-interstitial atoms, SIAs). The amount of radiation damage from these ballistic collisions is quantified 58-61 in terms of displacements per atom, dpa. A damage level of 1 dpa corresponds to “stable” displacement of every atom

from its lattice site. For reactor operating temperatures, there is sufficient thermally activated diffusion of the radiation-induced defects to enable recombination of many of the vacancies and SIAs so that the retained displacement damage is a fraction of the dpa value. A key strategy for designing radiation resistant materials is to promote very efficient recovery of the defects: Very little can be done to alter the instantaneous displacement damage from exposure to energetic neutrons, but substantial resistance to radiation damage can be engineered by efficiently facilitating the recombination of these defects. Considering that dimensional instabilities above a few percent generally cannot be tolerated in large-scale engineering structures and that future reactor designs call for structural materials that will be exposed to damage levels in excess of 100 dpa, the challenge is to engineer “self-healing” defect recombination processes into structural materials that are ~99.99 % efficient. A further challenge is that these engineered defect recombination structures must be resistant to the vigorous transient (~1 fs to 1 ps) atomic mixing that occurs within fast neutron-induced displacement cascades; the magnitude of this transient atomic mixing is roughly two orders of magnitude higher than the dpa value 58,60,61 and could result in dispersal or dissolution of nanoscale precipitate structures. Radiation damage poses five main threats to the operation of structural materials, emerging at different operating temperatures and damage levels 60,62 . These phenomena are summarized in Fig. 3. At low temperatures (below 0.3-0.4 T M , where T M is the absolute melting temperature), radiation-induced defect clusters (predominantly created directly in displacement cascades) serve as strong obstacles to dislocation motion. This radiation hardening is usually accompanied by substantial reductions in uniform elongation and macroscopic work hardening capacity, and can induce loss of fracture toughness in body

capacity, and can induce loss of fracture toughness in body Fig. 3 Summary of five radiation

Fig. 3 Summary of five radiation damage threats to structural materials performance.

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3 Summary of five radiation damage threats to structural materials performance. NOVEMBER 2009 | VOLUME 12

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centered cubic metals and alloys 63 . Since the radiation hardening emerges at relatively low doses (0.001 to 0.1 dpa), radiation hardening and embrittlement often defines the lower operating temperature limit for structural materials in neutron irradiation environments. At intermediate temperatures, three distinct radiation effects phenomena are of potential significance for doses above ~1 to 10 dpa: radiation- induced segregation and precipitation (0.3-0.6 T M ) that can lead to localized corrosion or mechanical property degradation such as grain boundary embrittlement 64 , void swelling from vacancy accumulation (0.3-0.6 T M ) that can create unacceptable volumetric expansion 65 , and radiation induced creep 65 and/or anisotropic growth 66 (0.2-0.6 T M ) that can produce dimensional expansion along directions of high stress and/or specific crystallographic directions. At very high temperatures (>0.5 T M ) and under applied mechanical stress, helium produced by neutron transmutation reactions in the structural material may migrate to grain boundaries and form cavities, thereby causing intergranular fracture with limited ductility in stressed materials 67 . This high temperature helium embrittlement of grain boundaries typically emerges for helium concentrations above 10 to 100 appm (~1 to 100 dpa depending on material and neutron spectrum) and becomes increasingly severe with increasing temperature and applied stress and decreasing deformation rate. Along with chemical compatibility and thermal creep strength, high temperature helium embrittlement may define the maximum allowable operating temperature for a structural material in neutron irradiation environments.

Structural materials issues for fission reactors: life extension of existing reactors and deployment of next generation reactors

Nuclear reactors represent a harsh environment for components, combining the effects of high temperature water, stress, vibration, and an intense neutron field. Degradation of materials in this environment can lead to reduced performance, or in severe cases, sudden failure. When polled during a recent Electric Power Research Institute study on the most challenging issues facing further life extension, two-thirds of the 47 US nuclear utility executives cited nuclear power plant reliability as the key issue, with materials aging and cable/piping degradation listed as the primary concerns. Materials degradation in a nuclear power plant is complex due to the wide variety of materials, environmental conditions, and stress states 68 . Over 25 different metal alloys can be found within the primary and secondary systems of today’s light water reactor fleet (cf. Fig. 1) and additional materials exist in the concrete containment vessel, instrumentation and control systems, cabling, buried piping and other support facilities. As a result, the dominant forms of degradation may vary greatly between different reactor systems, subsystems, and components. However, material degradation of any system can have an important role in the safe and efficient operation of a nuclear power plant. Routine surveillance and component

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replacement can mitigate these factors, although failures may still occur. Considering the potential for power uprates (resulting in higher operating temperatures) and for reactor life extensions to 60 years or beyond, many components must tolerate the reactor environment at temperatures near or slightly higher than their original design limit for very long times. This may increase the susceptibility to failure for some components and may introduce new degradation modes. While all components (except perhaps the reactor pressure vessel and concrete support structures) can be replaced, it may not be economically favorable. Therefore, understanding, controlling, and mitigating materials degradation processes are key priorities for reactor operation, power uprate considerations, and life extension. The Reactor Pressure Vessel (RPV) is the largest component in the pressure boundary of a light water nuclear reactor. It provides the primary line of defense against a release of radiation and the steels used for RPVs must maintain conservative margins of fracture toughness so degradation does not threaten the integrity of the RPV during either normal operation and maintenance cycles or under accident transients 69 . Neutron irradiation can degrade the fracture toughness of these steels and in some cases severely. Extending the operating lifetime of a reactor to beyond 60 years may require a careful evaluation of these irradiation-induced embrittlement effects 69 . Structural components within the reactor core (commonly 304 or 316 stainless steel) are often the most critical for safe and reliable operation as the failure of a core internal component may have very severe consequences. There are a number of key issues that must be considered and evaluated when considering extended reactor lifetimes, including thermal aging, fatigue, corrosion, and irradiation damage. The extended exposure of core internal components to elevated temperature may be sufficient to induce a variety of phase transformations and potentially reduce fracture toughness. Fatigue has been identified as a potential concern for existing service conditions for a number of different components and subcomponents 9 . Extension to longer service lifetimes may exacerbate the susceptibility to fatigue. Over a forty-year operating time period in a light water reactor, internal structural components may be exposed to fast neutron fluences up to ~10 22 n/cm 2 and ~10 23 n/cm 2 (E > 1 MeV) in a boiling- and pressurized-water reactor, corresponding to ~7 dpa and 70 dpa, respectively. Extending the service life of a reactor will increase the total neutron fluence to each component. Fortunately, radiation effects in stainless steel are relatively well known to high damage levels 24,65,68 , in part because these materials are also of interest for fast-spectrum fission and fusion reactors that require operation to very high fluence. Allen and Busby recently reviewed key modes of irradiation-induced degradation of structural materials for light water reactors and concluded that the effects of radiation-induced segregation, swelling, and/or precipitation may require the most evaluation for continued operation 70 .

Structural materials for fission & fusion energy

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In addition to elevated temperatures, intense neutron fields, and stress, components must also be able to withstand a corrosive aqueous environment 71 . The presence of stress may also promote varying forms of stress-corrosion cracking (e.g. irradiation-assisted stress corrosion cracking, primary water stress corrosion cracking, etc). Since the operating corrosion mechanism generally varies with location in the reactor coolant circuit, a number of different mechanisms may be operating at the same time. Clearly, even moderate rates of corrosion are not acceptable for the safe and reliable operation of a reactor under extended lifetime conditions. As a result, the various corrosion mechanisms must all be understood and evaluated for different reactor components and sub-systems to ensure safe extended service. For advanced future fission reactor systems such as proposed Generation IV reactors, structural material performance and integrity are just as important and likely even more complex than light water reactor applications 24,27,72-77 . Qualifying a material for service in

a liquid metal, molten salt, or gas environment would be based on

principles similar to those in water reactors. While the material of choice may be a different alloy (or even ceramic), the material must still have well-established and high-performance mechanical properties (including good thermal creep resistance), long-term phase

stability, and compatibility 78 with the reactor coolant. It must also be able to pass the licensing process and be supported by an extensive and reproducible set of data on relevant properties. Finally, since the materials could be used in an intense high-energy neutron field,

it must exhibit good dimensional, mechanical and microstructural

stability to neutron displacement damage. The radiation-resistance

is often the most challenging requirement to evaluate since the

key degradation mechanisms are sensitive to the specific radiation conditions. Fig. 4 compares the proposed operating temperatures and lifetime displacement damage levels for structural materials in the six Generation IV concepts and three fusion energy systems with the existing knowledge base.

fusion energy systems with the existing knowledge base. Fig. 4 Overview of operating temperatures and displacement

Fig. 4 Overview of operating temperatures and displacement damage dose regimes for structural materials in current (generation II) and proposed future (Generation IV) fission and fusion energy systems. The six Gen IV fission systems are Very High Temperature Reactor (VHTR), Super Critical Water Reactor (SCWR), Lead Fast Reactor (LFR), Gas Fast Reactor (GFR), Sodium Fast Reactor (SFR), and Molten Salt Reactor (MSR).

A pathway to improved structural materials for fission and fusion energy.

Existing structural materials have rather limited operating temperature regimes where they can be utilized in a neutron irradiation environment 30,79 , as summarized in Fig. 5 for moderate damage levels of 10 to 50 dpa. At low temperatures, the reduced ductility associated with low temperature radiation hardening creates conditions where modified (larger safety margin) engineering design rules must be used 80 . In cases where fracture toughness is reduced by low temperature irradiation, the operating temperature is restricted to higher temperatures where embrittlement does not occur for anticipated normal and transient operating conditions. The upper operating temperature limit is typically determined by thermal creep strength or high temperature helium embrittlement considerations. Advanced materials can enable improved reactor performance via increased safety margins and design flexibility, in particular by providing increased tensile strength, thermal creep resistance and superior neutron radiation damage resistance. A key strategy for designing high-performance radiation-resistant materials is based on the introduction of a high, uniform density of nanoscale particles that simultaneously serve as obstacles to dislocation motion (providing high strength) and point defect recombination centers (providing good radiation damage resistance) 29,39-41,45,81-86 . Development of structural materials for large-scale energy application is historically a long and costly process, due to the extended period to develop a new alloy followed by an even longer proof testing period to validate the performance of the material in prototypic environments for appropriate licensing authorities. For example, Fig. 6 shows the historical rate of progress in improving the upper operating temperature limit of steels for general (non-nuclear) structural applications has averaged ~2.5 °C/year for the past 60 years 87 . Materials science tools such as computational thermodynamics and multiscale radiation damage computational models, in conjunction

radiation damage computational models, in conjunction Fig. 5 Estimated operating temperature windows (dark shaded

Fig. 5 Estimated operating temperature windows (dark shaded region) 30,79 for structural materials in nuclear energy systems for damage levels of 10 to 50 dpa. The light blue and red regions represent lower and upper temperature uncertainty bands.

NOVEMBER 2009 | VOLUME 12 | NUMBER 11

blue and red regions represent lower and upper temperature uncertainty bands. NOVEMBER 2009 | VOLUME 12

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Structural materials for fission & fusion energy

REVIEW Structural materials for fission & fusion energy Fig. 6 Historical rate of improvement in the

Fig. 6 Historical rate of improvement in the maximum operating temperature for four generations of structural steels, based on results summarized by Viswanathan 87 .

with focused experimental validation studies (nonirradiation and irradiation environments), may offer the potential to reduce the time period to develop and qualify structural materials for advanced nuclear energy systems. It is worth noting that many structural materials currently being used in fission reactors are based on alloys that were originally developed in the 1950s and 1960s. There are numerous examples where high-performance materials are being developed with the assistance of modern materials science tools 37,41,81-84,86,88-90 . For example, first principles atomistic modeling results 91 provided important insight that the formation of highly stable nanoscale clusters enriched in Y, Ti and O from initial Y 2 O 3 and Fe-Ti master alloy powders in a nanocluster-strengthened ferritic steel may have been enabled by the high concentration of vacancies produced during ball milling as part of the powder metallurgy processing of this steel. This nanocluster-strengthened ferritic steel has exhibited very high strength and good fracture toughness down to 120 K, and did not exhibit the sharp degradation in fracture toughness following neutron irradiation to moderate doses near 300 °C that caused embrittlement in conventional ferritic/martensitic steel 44,92 . Similarly, ultra-high strength precipitation-hardened steels with adequate fracture toughness have recently been developed by carefully controlling the formation of fine-scale (Mo,Cr) 2 C precipitates 93 . Fig. 7 compares the fracture toughness versus tensile strength behavior for the Aermet precipitation-strengthened steel 93 and the 14YWT nanocluster- strengthened steel 92 with the behavior for conventional bainitic and ferritic-martensitic steels. In all steels, the classic tradeoff between high strength and high toughness is evident. However, the critical tensile strength above which fracture toughness is reduced to low values is approximately 700 MPa in the conventional steels, whereas it is nearly 2000 MPa in the nanocluster-strengthened and fine-scale (Mo,Cr) 2 C strengthened steels.

18

and fine-scale (Mo,Cr) 2 C strengthened steels. 18 NOVEMBER 2009 | VOLUME 12 | NUMBER 11

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steels. 18 NOVEMBER 2009 | VOLUME 12 | NUMBER 11 Fig. 7 Tradeoff between fracture toughness

Fig. 7 Tradeoff between fracture toughness and tensile strength for conventional and advanced 92,93 steels.

This suggests that it may be possible to develop alloys with substantially improved mechanical properties compared to conventional alloys by appropriate use of either evolutionary ingot- based steel metallurgy or alternative processing techniques such as powder metallurgy production of oxide dispersion strengthened steels. In either approach, development of a high density of thermally stable, nanoscale hardening centers produces good mechanical properties. The 14YWT nanocluster-strengthened alloy also exhibits very good high temperature particle stability and thermal creep strength 94 , and has demonstrated good resistance to low-temperature neutron irradiation embrittlement in preliminary low-dose irradiation tests. Limited success has also been obtained in creating high strength structural alloys that simultaneously convey improved high temperature oxidation resistance 86 . The prospect of developing new corrosion-resistant high-performance structural alloys tailored for specific coolants and operating regimes is an exciting goal worthy of future research. Additional comprehensive validation of the performance of these types of advanced structural materials in prototypic operating environments will be a key step to obtain acceptance of these advanced materials by reactor vendors, utilities, and licensing authorities.

Conclusions

In order for fission and fusion energy systems to reach their full potential, high performance structural materials are needed that encompass improved mechanical strength, adequate ductility and fracture toughness, good radiation resistance, and corrosion resistance. Development of a high density of uniformly distributed nanoscale hardening centers that are stable to thermal coarsening and radiation-induced growth or shrinkage is a conceptually attractive method to create a high-performance radiation resistant material. Emerging results from several classes of ferritic and austenitic steels suggest that substantial improvement

Structural materials for fission & fusion energy

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in the performance of structural materials might be achievable. Considerable experimental validation will be needed to demonstrate the superior stability of these new alloys under prolonged exposure to high

temperatures, mechanical stress, and neutron irradiation.

temperatures, mechanical stress, and neutron irradiation. Acknowledgments This work was sponsored in part by the Light

Acknowledgments

This work was sponsored in part by the Light Water Reactor Sustainability Research and Development program, Office of Nuclear Energy and by the Office of Fusion Energy Sciences, U.S. Department of Energy.

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Discovery and design of nuclear fuels

To facilitate the discovery and design of innovative nuclear fuels, multi-scale models and simulations are used to predict irradiation effects on properties such as thermal conductivity, oxygen diffusivity, and thermal expansion. The multi-scale approach is illustrated using results on ceramic fuels, with a focus on predictions of point defect concentration, stoichiometry, and phase stability. The high performance computer simulations include coupled heat transport, diffusion, and thermal expansion, and gas bubble formation and evolution in a fuel element consisting of UO 2 fuel and metallic cladding. The second part of the paper is dedicated to a discussion of an international strategy for developing advanced, innovative nuclear fuels. Four initiatives are proposed to accelerate the discovery and design of new materials:

(a) Create Institutes for Materials Discovery and Design, (b) Create an International Knowledgebase for experimental data, models (mathematical expressions), and simulations (codes), (c) Improve education and (d) Set up international collaborations.

Marius Stan Los Alamos National Laboratory, Los Alamos, NM 87545, USA. Email: mastan@lanl.gov

Nuclear fuels are complex, multi-component materials containing actinides such as Th, U, Np, Pu, Am, Cm and their compounds in specific fuel forms (oxides, nitrides, carbides, alloys, composites, etc). Adding to the complexity and creating time-varying composition, the presence of fission products such as Xe, Cs, Sr, He, I, and Tc makes understanding the evolving properties of nuclear fuels a major challenge. For example, sintering of ceramic

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a major challenge. For example, sintering of ceramic 20 NOVEMBER 2009 | VOLUME 12 | NUMBER

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fuels requires a strict control of composition, thermal treatment, pressure, and atmosphere 1-3 . The large number of control parameters and the uncertainty associated with them often leads to intractable problems. Similar issues impact the casting and stability of metallic fuel rods 4,5 . Once in the reactor, the fuels and structural materials (pressure vessels, pipes, ducts, etc.) are subjected to radiation environments that continuously alter their

ISSN:1369 7021 © Elsevier Ltd 2009

Discovery and design of nuclear fuels

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Box 1. Scientific discovery and design of materials

The definitions below are only intended to clarify the use of various concepts in this paper. For this purpose, science is defined as a rigorous, systematic use of observations and logic to support or falsify possible explanations of natural phenomena. This is not that different from the Britain’s Science Council definition, discussed in 15 . The scientific method of investigating natural phenomena (recently under serious and loving scrutiny 16 ) consists of a series of steps that involve experimental, theoretical, and computational methods. An experiment is a procedure undertaken to make a discovery, test a hypothesis, or demonstrate a known fact. This concept is strongly anchored in immediate reality although recently the concepts of “computer experiment” and “virtual experiment” have gained some popularity. A theory is a formal statement of ideas which are proposed to explain a class of facts or events. Computation is a procedure used to determine the solution of a mathematical problem by means of a computer.

Although the scientific method is observed, to various degrees, by the entire materials science community, there are notable differences in the scope and methodology, depending on the goal of the research, the resources, and the scientific or engineering targets. Materials discovery (see 17 as an example) involves exploring and identifying existing materials with desirable properties and functionality. The emphasis is on conducting sound research in areas that are likely to lead to materials with outstanding properties. As with any other discovery enterprise, being capable and ready to identify the value of specific results is the key. Materials design (see 18 as an example) aims at creating new materials with predefined properties and functionality. After defining the properties of interest, the focus is on optimizing specific parameters of existing materials or creating completely new materials that exhibit the sought after properties. The design methodology (Fig. 1) is quite cumbersome and involves a series of steps and iterations that may or may not converge toward a set of optimal parameters.

thermo-mechanical properties 6-10 . It is well documented 11 that fuels exhibit radial and angular cracks and the severity of the structural damage increases with burnup. Root causes of these phenomena are fission-product migration and accumulation in gas bubbles 12-14 that create porosity and significantly slow down the transport of heat. To create improved nuclear fuels for the next generation of reactors, scientists and engineers are partnering in research and development work that follows the steps of the scientific method. Modern materials, including nuclear fuels, are often developed using a combination of discovery and design (see Box 1), with a certain emphasis on discovery. To facilitate the discovery and design of innovative nuclear fuels and structural materials, models and simulations are used to predict irradiation effects on properties such as formation of point defects and clusters 19-27 , chemical species and fission-product migration 28-31 , gas bubbles formation 32 , thermal conductivity 33-35 , oxygen diffusivity 36,37 , dislocations 38-41 , thermal expansion 42 , and phase stability/ transformations 43,44 . One of the most challenging aspects is modeling the complex electronic structure of materials in general 45 , and the actinides (especially Pu) in particular 46,47 as well as the stability of their phases 48 . Another challenge is modeling high temperature effects such as entropic contributions to the free energy of liquids 49 .

Conventional nuclear fuels

Recent applications of a multi-scale methodology (see Box 2) to oxide nuclear fuels resulted in predictions of irradiation effects on properties such as thermal conductivity, oxygen diffusivity, and thermal expansion. The methods cover a large spectrum of time and space scales, from electronic structure to atomistic, to meso-scale, to continuum 55 .

to atomistic, to meso-scale, to continuum 5 5 . Fig. 1 The materials design methodology involves

Fig. 1 The materials design methodology involves a series of steps, iterations, and periodic feedback between theory, experiment, and computation.

For example, atomistic models of point defect have been used to develop continuum thermo-chemical models of point defect concentrations and oxygen diffusivity in uranium oxides 19 and plutonium oxides 56 . Several models include the dependence of the properties on the oxygen content. Building on thermochemical studies 57-59 , the models are further used to predict fuel thermodynamic properties such as the free energy, and to simulate oxygen diffusion at various temperatures and oxygen pressures. Another example, this time at the meso-scale, is related to phase- field simulations of gas bubbles formation and evolution in the fuel 60 .

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field simulations of gas bubbles formation and evolution in the fuel 6 0 . NOVEMBER 2009

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Discovery and design of nuclear fuels

Box 2. Multi-scale models and simulations

This section builds upon a recent discussion of modern epistemic concepts 42 . A model is a logical description of how a system (material, in our case) performs. Models can be empirical or theory-based. Empirical models are collections of experimental observations fitted to mathematical expressions, such as (but not only) polynomial functions. When accurate, empirical models are highly valuable for technological applications. Theory-based models are built upon fundamental principles developed within or across scientific disciplines (physics, chemistry, etc). The multi-science models avoid trial-and-error exercises and aim at providing a deeper understanding of material’s (fuel’s) behavior. Theory- based models are expected to have better predictive character. A simulation is the process of conducting experiments or running computer programs to reproduce, in a simplified way, the behavior of a system (nuclear fuel, in our case). Simulations describe the evolution of the system along a certain coordinate, most often the time (correlated with the burnup level for the case of nuclear fuels). Both the models and the simulations must be subject to verification and validation 50 . Verification is the process by which the fidelity of a numerical algorithm with respect to underlying mathematical

representation of a model or simulation is established and the errors in its solution are quantified. Validation is the process through which the scientific community comes to accept that a particular model or simulation reliably describes real world behavior. Most validation processes involve comparison with experimental data. A critical component, uncertainty quantification is the process of characterizing and reducing uncertainties of measurements, model predictions, and simulation results. To account for all the important materials properties and reactor phenomena, the multi-scale models and simulations must address a wide range of space and time scales, starting with the nucleus and the atomic electronic structure (nm) all the way to the reactor components (meters), and from defect formation (pico-seconds) to the operating characteristic times (months, years). Fig. 2 illustrates some of the theoretical and computational methods used in the multi-scale approach 42,51-53 . The information is transferred between scales via characteristic parameters such as density, energy, temperature, or grain size distribution 54 . Meso- scale and continuum methods are often “atomistically informed”, in the sense that some of the parameters in the methods are optimized against the output of atomistic calculations.

are optimized against the output of atomistic calculations. Fig. 2 Multi-scale theoretical and computational methods

Fig. 2 Multi-scale theoretical and computational methods used for materials model development and computer simulations.

Fig. 3 shows a comparison of experimental 61 and simulation 62 results.

The simulations capture well the nucleation, growth, and coalescence

of gas bubbles in the fuel grains and at the grain boundaries. The

simulations also predict the thermal conductivity dependence on the

porosity associated with the gas bubbles and the impact on the heat

release.

Similar results have been reported on PuO 2 fuels 56,63,64 . Although

not as extensive, the work on other ceramic fuels such as nitrides 65,66

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or carbides (with application to coated particle fuels 67,68 ), as well as

studies of surrogate materials based on cerium 69 or dysprosium 66 are

most encouraging.

Fuel performance (see Box 3) is another area that has benefited

from advanced models and simulations 70 . Understanding complex

phenomena in fuel elements provides important input to reactor

simulations, currently based on homogenization techniques 77 . Recent

studies have examined in more detail the thermochemistry of the

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BOX 3. Fuel performance capabilities

A fuel performance capability (FPC) consists of a computer code or

a set of codes that contain models of fuel properties and are able to

simulate phenomena in the nuclear fuel during operation 71,72 . In a

more general version of this concept, the fuel performance is evaluated

in the entire fuel element (fuel plus clad) and validated “in-pile” 73 . In

addition to experimental Post Irradiation Examination (PIE), the fuel performance capabilities are increasingly complex tools in support of fuel characterization and optimization. A preliminary design of a new generation Advanced Fuel Performance Capability (AFPC) was recently proposed 42 . To

address the nuclear fuels material properties and phenomena, the capability includes specific computational modules and interacts with an external database that is continuously updated with the most advanced models of fuel and materials properties and the necessary nuclear data. To achieve a consistent predictive character, many such capabilities are moving away from empirical models and include theory based models 65,70 . Other requirements are related to numerical algorithm design, uncertainty quantification, and software engineering, including

the use of nested (linear + non-linear) solvers 74,75 , multi-level preconditioning, running parallel on large-scale supercomputers, and easy adaptation to heterogeneous computational platforms. Fig. 5 shows various paths for fuel performance code development, using as starting point the USA empirical codes FRAPCON and LIFE. The blue line represents the path of using “of the shelf” Advanced Scientific Computing Initiative (ASCI) codes that have been developed at national laboratories for national security applications, followed by the addition of physics-based models specific to nuclear fuels. The red line represents the path chosen by scientists who are interested in first testing the science-based models in commercial codes such as Comsol and Abaqus, and only later migrating the codes to high-performance computers. The best solution might be a balanced approach to designing a new fuel performance code (green line), based on the experience accumulated by the European scientists in developing Transuranus and Pleiades. As the predictive capabilities continue to improve, fuel performance codes are expected to become an integral component of nuclear fuels design and licensing, and of nuclear waste certification processes 76 .

and of nuclear waste certification processes 7 6 . Fig. 3 Top: Fission gas bubbles in
and of nuclear waste certification processes 7 6 . Fig. 3 Top: Fission gas bubbles in

Fig. 3 Top: Fission gas bubbles in UO2 irradiated in a Pressurized Water Reactor at burnup level 25GWd/t. The sample was annealed at 1275 ºC for 5 hours. Bottom: Phase Field simulations of gas bubble evolution.

fuel-clad interactions 78,79 and the influence of temperature and fuel

stoichiometry changes on the coupling of heat and species transport in

a UO 2 fuel element with stainless steel clad 80 . The results show that

the counterbalancing of the Soret and Fickian fluxes is responsible for

the variation of oxygen concentration in the fuel pellet. Furthermore,

the simulations demonstrate that including the dependence of thermal

conductivity and density on non-stoichiometry can lead to changes

in the calculated centerline temperature that exceed 100 K (Fig. 4).

Additional simulations involved transient regimes and the examination of

the time lag in the response of the temperature and non-stoichiometry

distributions with respect to sudden changes in heat generation rate and

oxygen removal rate. Current work at Los Alamos includes studies of the

effects of porosity on thermal conductivity and thermal expansion 81 , and

simulations of clad deformation.

Advances in theoretical, experimental and computational capabilities

Addressing the materials challenges requires a closely coupled

experimental, theoretical, and computational effort directed at

both the scientific and the engineering issues. In this partnership,

new experimental investigation methods such as synchrotron light

sources and proton radiography increase the potential of “in-situ”

characterization of radiation effects on nuclear fuels and provide new

validation opportunities. In addition, theory and high performance

computing expand the investigation space to identify and resolve new

scientific problems.

All top 500 fastest supercomputers in the world can now reach

over a teraflops (10 12 operations per second) and the number of

petaflop (10 15 operations per second) supercomputers is increasing

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Discovery and design of nuclear fuels

REVIEW Discovery and design of nuclear fuels Fig 4. Simulation of heat transport in a UO

Fig 4. Simulation of heat transport in a UO 2+x fuel element with metallic clad. The temperature profile demonstrates that including the stoichiometry x in the thermal conductivity model changes the predicted centerline temperature by more than 100 K.

at a fast pace 82 . Already, neutron diffusion calculations, as well as some reactor hydrodynamics simulations 83,84 are being performed on such resources. As exaflop computers (10 18 operations per second) are being designed, there is a tremendous opportunity for involving high-performance computing in nuclear fuels design. However, high-performance computing requires far more than high-speed computing. It requires science-based models, innovative numerical methods, and the ability to generate new ideas 85 . Here are a few predictions of exascale computing results and how they can spark transformational science in support of nuclear fuels discovery and design:

• Quantum Mechanical calculations of electronic structure properties of systems consisting of trillions of atoms, compared to the current hundreds of atoms. Such simulations will predict properties such as free energy of formation of multi-component metallic and ceramic fuels.

• Quantum Mechanical calculations at finite (room, high) temperature, in contrast to the current (mostly) 0 K results. This will enable predictions of properties such as phonon spectra, heat capacity, bulk moduli, and stress-strain curves in temperature regimes relevant to manufacturing, operation, and storage of nuclear materials.

manufacturing, operation, and storage of nuclear materials. Fig. 5 Classification of some of the codes currently

Fig. 5 Classification of some of the codes currently used for fuel performance and paths towards designing a new generation fuel performance capability.

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and paths towards designing a new generation fuel performance capability. 24 NOVEMBER 2009 | VOLUME 12

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Discovery and design of nuclear fuels

REVIEW

• Atomistic (e.g. Molecular Dynamics) simulations of a much larger number of atoms (10 20 ), compared to the current state of the art (10 8 ). Such capability will allow for simulations of radiation effects and damage in heterogeneous regions of the fuel, such as grains and interfaces.

• Atomistic simulations (e.g. coupled Molecular Dynamics and Monte Carlo) of coupled neutron transport and radiation cascades in systems consisting of trillions of atoms, for hours or even days. This will open up an unprecedented investigative space to include: simulations of fission-products diffusion in the grain and at the grain boundary, gas bubbles nucleation, and swelling. It will also enable access to critical phenomena such as stress corrosion cracking 86 .

• Meso-scale diffuse-interface (phase-field) or sharp-interface (level- set) simulations of microstructure evolution under irradiation. These simulations will most likely be “atomistically informed” and will include defect formation and recombination processes occurring in radiation cascades. These simulations will assist the optimization of advanced, innovative nuclear fuel forms and the design of radiation resistant structural materials.

• Multi-scale, embedded simulations, covering large time and space domains. Such simulations will improve on the “first principles” character of the multi-scale methodology. However, including all atoms in the simulation of a specific reactor component is not only impossible but is also undesirable. Developing comprehensive models and running simulations “at

comprehensive models and running simulations “at Fig. 6 Schematic representation of the main components of an

Fig. 6 Schematic representation of the main components of an Institute for Materials Discovery and Design (IMDD).

scale” in sync with a smart transfer of information between scales remains the best approach.

Innovative nuclear fuels

Discovery and design will play a crucial role in developing innovative nuclear fuels and structural materials for the new generations of fission and fusion reactors 87-91 . Besides the optimization of the current fabrication methods, high performance computing will open many doors to investigating new phenomena in materials. Advances in theory, experimental techniques, and computational science will lead to completely new ways of doing science. What will be next? How about building materials “atom by atom” to create structures capable of accommodating the local radiation environment? How about “self- healing” nuclear reactors that recover after accidents? The range of innovative science is only limited by our imagination. An integral component of the innovative fuel development is the understanding of thermal, mechanical, and chemical properties of the fissile materials, the source of energy in a nuclear reactor. The multi- scale approach described in the previous section for U-Pu fuels can be extended to multi-component systems containing Th (ThO 2 based fuels are already here 92 ), Am (already in some mixed oxide fuels 93 ), Np, Cm and their mixtures, in fuel forms such as ceramics, alloys, and composites. That requires several essential steps:

• Developing theory-based models of the free energy of the subsystems, such as the binary and ternary phases.

• Developing theory-based models of the mobility of species (actinides, fission products, oxygen, nitrogen, etc).

• Performing simulations of coupled thermal and neutron transport, species diffusion, and deformation in the multi-component materials that are major candidates for innovative fuels.

Such a study is extraordinarily complex, requires a tremendous amount of work, and should start now. It takes years to develop a good understanding of the properties and phenomena in new, multi- component materials. One of the goals that bring together the scientific and engineering communities is to control the properties and phenomena in irradiated nuclear fuels and materials. As shown in the previous sections, to achieve this goal the international community must engage in developing theory-based models that enhance the understanding of irradiation effects on materials properties and developing the computational science required to perform high-performance simulations. Another important goal is to discover or design new, innovative fuels and materials for nuclear energy applications. That involves creating an integrated theoretical, experimental, and computational validation process and engaging the national and international communities in solving problems of high complexity.

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national and international communities in solving problems of high complexity. NOVEMBER 2009 | VOLUME 12 |

25

REVIEW

Discovery and design of nuclear fuels

Achieving these goals requires a new paradigm that favors a much stronger coupling of the various components of the multi-scale model and simulation methodology as well as a new level of collaboration and integration among experimentalist, theorists, and computational scientists. The sub-sections below outline a few components of a strategy intended to increase the chances of both controlling properties and discovering and/or designing better nuclear fuels and structural materials for the new generations of nuclear reactors.

Institutes for materials discovery and design

Creating national and international institutes (centers, hubs, etc) dedicated to accelerating the discovery and design of improved materials is an immediate and potentially most rewarding initiative. The mission of such centers is to provide the scientific environment and resources (people, supercomputers, and funding) for the development of theory-based models, simulations, and computational tools able to assist the discovery and design of nuclear fuels and structural materials. The institutes will bring together scientists that are trained in all three areas: experiment, theory, and simulation, and experts in one. The model development work will cover a wide range of space and time scales requiring a well balanced portfolio of expertise. The participants will collaborate in developing and performing atomistic, meso-scale, and continuum simulations of irradiation effects and transport phenomena in reactor materials, to predict and control point defect formation, microstructure evolution, and materials performance in reactor environments. The centers will include state of the art laboratories for small- scale experiments, computational materials science hubs for model development and remote simulations on high-performance computers, meeting rooms equipped with advanced visualization capabilities, and offices for staff, guest scientists and students (Fig. 6). It is critical for IMDDs to bring together both mature and early career scientists, in a work environment that allows for uninterrupted time for science.

Knowledgebase for data, models, and simulations

Every day, a tremendous amount of data is created as a result of performing experiments and running simulations. Besides numerical data storage, analysis, and retrieval much progress was made on the management of information regarding models (mathematical expressions), simulations (codes), and the visual representations of their results (pictures, animations). As a consequence, creating, updating, and maintaining an international “knowledgebase” that includes experimental data, models (mathematical expressions), and simulation results (tables, graphs, diagrams), all linked to publications and web sites, is now possible. The knowledgebase will have a user-friendly interface and will use advance query techniques capable of retrieving numbers, text, and images. The

26

capable of retrieving numbers, text, and images. The 26 NOVEMBER 2009 | VOLUME 12 | NUMBER

NOVEMBER 2009 | VOLUME 12 | NUMBER 11

knowledge-base will be updated with information from the IMDDs and will serve as a resource for national laboratories, universities, and companies. No doubt that such an effort will face numerous challenges, especially in the area of proprietary information, licensing of fuel performance codes, and non-proliferation. There is however a significant amount of fundamental scientific information, such as thermal, mechanical and chemical properties of generic multi- component fuels and structural materials, phase stability (phase diagrams), and transport (diffusion) of elements, that can be shared without infringing upon restricted data.

Education

The most important resources for creating innovative nuclear fuels are the nuclear engineers, materials scientists, physicists, chemists, computers scientists, etc. Their contribution is essential in advancing the integrated experimental, theoretical, and computational work and they are the supreme validation authorities. In recent years, the nuclear engineering community has taken steps toward engaging prestigious scientists in nuclear fuels research via conferences and workshops. Scientists are often tempted to direct their studies toward the most interesting and challenging scientific areas rather than the most technologically relevant ones; their attraction to nuclear energy research is rooted in curiosity. To increase the scientific interest, well- funded national programs must be created to support fundamental science in the area of nuclear energy and increase the likelihood of breakthrough discoveries and creative design. Computational scientists and software engineers are major participants in designing and writing fuel performance codes. However, strong teaming among engineers, scientist, and software developers is key to creating science-based, high-performance codes capable of running on the present petaflop and the future exaflop computational platforms. To expand and improve the quality of the models and simulations, the international nuclear fuels community must develop a large pool of experts to cover the necessary theoretical, experimental, and computational tasks. That can be achieved by including “Models and Simulation of Nuclear Fuels and Structural Materials” in the materials science and nuclear engineering programs at universities across the world. The involvement of the national and international decision factors (politicians and managers) in the scientific meetings is an encouraging recent development. More and more decision factors are becoming aware of the scientific and computational challenges faced by the nuclear fuels community and can better provide guidance and financial support for the future research and development programs.

International collaborations

In addition to improved experiments, models, simulations, and computational capabilities, a coherent nuclear energy program requires

Discovery and design of nuclear fuels

REVIEW

national and international collaborations. To cover the necessary areas of expertise, organizing workshops and sessions on models and simulations of nuclear materials at international conferences is a natural strategy component. Only two of the many important scientific meetings in this area are discussed below. The Materials Models and Simulations for Nuclear Fuels (MMSNF) workshop series aims at stimulating discussions and research to advance theory-based model development, high-performance computer simulations, and experimental validation for nuclear fuels applications. The workshops series started in June 9-10, 2003 in Santa Fe, NM, USA with support from the Advanced Fuel Cycle Initiative program, funded by the USA Department of Energy, and the Los Alamos National Laboratory. The workshops usually bring together around fifty experts in experiments, theory, and models and simulations from twelve countries or more. The most recent edition of the workshop (Albuquerque, USA) resulted in an evaluation of atomistic, meso-scale, and continuum simulation methods and their impact on nuclear fuel design. The next edition (MMSNF-9) will be part of the Nuclear Materials Conference, NuMat 2010, in Germany. The Working Party on Multi-scale Modelling of Fuels and Structural Materials for Nuclear Systems (WPMM) was created in January 2008, with guidance and support from the Nuclear Energy Agency (NEA), to address scientific and engineering aspects of fuels and structural materials. The main goal of WPMM is to establish multi- scale models and simulations as validated predictive tools for the design of nuclear systems, fuel fabrication, and fuel performance. The main tasks include: identification of fundamental problems, development of atomistically-informed models and simulations of nuclear fuels and structural materials properties, promoting high performance computer simulations, and maintaining synergy with experimental work. Validation of simulation and model predictions is also a priority as well as the development of new applied mathematics and software tools. More initiatives of this type are needed to increase the quality and intensity of the debate over scientific and engineering problems relevant to nuclear fuels (including spent fuels 94 ) and nuclear energy in general 95 . In many areas, such as the thermo-mechanical and chemical properties of the fuels, the number of components of the system subject to investigation is so large (thousands) that no country alone can study all of them in a reasonable timeframe. Partition of work and good international collaboration form the best strategy for increasing the understanding and controlling the properties of such materials.

Summary and outlook

New generation, innovative nuclear fuels will be complex, multi- component systems that must perform well in the radioactive and corrosive reactor environment. The development of such fuels involves scientific methods focused on both discovery and design. In this context, multi-scale models and simulations are capable of investigating a wide range of space and time scales and interact with fuel performance capabilities to create complex tools in support of fuel characterization and optimization. In particular, high performance computing can contribute to increasing the predictive character of models and simulations and can inspire new ways of doing science. This approach is expected to become an integral component of nuclear fuels design, licensing, and waste certification processes. A new strategy for nuclear fuel development, that involves discovery and design as equal partners and drivers, is discussed in this paper. The strategy promotes a much stronger coupling of the various components of the multi-scale model and simulation methodology and a much stronger collaboration and integration among experimentalist, theoreticians, and computational scientists. To this end, it is important to create research institutes for materials discovery and design and to create and maintain an international knowledgebase for data, models, and simulation results. The strategy advocates for direct interactions among scientists, engineers, and decision factors (politicians and managers) via international workshops and conferences. Such initiatives, complemented by other ideas from the international community, will provide the framework for a stronger integration of theory, experiments and simulations, leading to an improved control of the properties and phenomena in reactor materials, and the discovery

and design of new, innovative nuclear fuels and structural materials.

of new, innovative nuclear fuels and structural materials. Aknowledgements This work was occasionally supported by the

Aknowledgements

This work was occasionally supported by the U. S. A. Department of Energy via the Advanced Fuel Cycle Initiative (AFCI), the Global Nuclear Energy Partnership (GNEP), and the Nuclear Energy Advanced Models and Simulations (NEAMS) Programs.

Further information

Interesting web pages:

MMSNF-7: http://itu.jrc.ec.europa.eu/index.php?id=36&type=&iEntryU

ID=164&iEntryPID=68

NEA: www.nea.fr Roadrunner supercomputer: www.lanl.gov/roadrunner/ High Performance Computing workshop: www.cels.anl.gov/events/ workshops/extremecomputing/nuclearenergy/agenda.php.

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Nuclear reactor materials at the atomic scale

With the renewed interest in nuclear energy, developing new materials able to respond to the stringent requirements of the next- generation fission and future fusion reactors has become a priority. An efficient search for such materials requires detailed knowledge of material behaviour under irradiation, high temperatures and corrosive environments. Minimizing the rates of materials degradation will be possible only if the mechanisms by which it occurs are understood. Atomic-scale experimental probing as well as modelling can provide some answers and help predict in-service behaviour. This article illustrates how this approach has already improved our understanding of precipitation under irradiation, corrosion behaviour, and stress corrosion cracking. It is also now beginning to provide guidance for the development of new alloys.

Emmanuelle A. Marquis 1 *, Jonathan M. Hyde 1,2 , David W. Saxey 1 , Sergio Lozano-Perez 1 , Vanessa de Castro 1 , Daniel Hudson 1 , Ceri A. Williams 1 , Samuel Humphry-Baker 1 and George D.W. Smith 1

1 Department of Materials, University of Oxford, Parks Road, Oxford, OX1 3PH, UK

2 National Nuclear Laboratory, B168 Harwell, Didcot, Oxon OX11 0QJ, UK * Email: emmanuelle.marquis@materials.ox.ac.uk

There has been significant renewed interest in nuclear energy because of the pressing need to respond to the increasing worldwide energy demand whilst addressing climate change. Many of the current generation of fission nuclear reactors are seeing their use extended beyond the original 40 years lifetime despite the risks associated with materials aging. Consequently new plants need to be designed which are more efficient, more economical and safer. Generation IV (Gen IV) fission nuclear reactors will be responding to this economic need by optimizing use of natural resources, improving safety systems and reducing waste production 1 . In the longer term, fusion energy

30

production 1 . In the longer term, fusion energy 30 NOVEMBER 2009 | VOLUME 12 |

NOVEMBER 2009 | VOLUME 12 | NUMBER 11

is also extremely attractive with no generation of carbon dioxide or long lived radio isotopes and potentially limitless energy production. An experimental reactor, the Joint European Torus, is currently running in the UK and ITER 2 is to be built in France by 2020. ITER is an internationally-supported project, intended to be a large scale demonstration of the feasibility of producing energy by fusion. The next step, DEMO, aims at a sustainable production of fusion energy by 2040 3 . Whilst a significant amount of work has been devoted to fusion plasma physics, much less effort has focused on developing the infrastructure required to build these reactors and develop materials

ISSN:1369 7021 © Elsevier Ltd 2009

Nuclear reactor materials at the atomic scale

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able to withstand to the more extreme operating conditions associated with Gen III, Gen IV and fusion reactors. Whether materials are designed for Gen IV fission or fusion reactors, the requirements are similar: good tensile and creep strength, as high as possible operational temperatures, a low ductile to brittle transition temperature, resistance to irradiation, high thermal conductivity, low residual activation, compatibility with cooling media, and good weldability 4-6 . It is anticipated that the blanket structures of DEMO, will have to sustain doses of the order of >50dpa/ year 7 , accompanied by the introduction of ~10 appmHe/dpa and 45 appmH/dpa, as compared to a maximum of ~1dpa/year and 0.2-0.3 appmHe/dpa in current fission reactors. For improved thermodynamic efficiency, structural materials will need to operate at temperatures above 350, 390 or 600 °C for Gen IV reactors depending on their design 6 and above 500 °C for fusion reactors. Although the detailed designs of these reactors differ, in each case similar microstructural issues will need to be addressed, particularly materials degradation due to accelerated phase decomposition, accumulation of defects and accelerated corrosion kinetics. The development of new alloys has in the past relied on empirical approaches and it is clear that these methods are very valuable to select materials based on their tensile or fracture resistance performance. However, in order to have confidence in the safety and durability of reactor materials, a fully mechanistic insight into the evolution of microstructures when materials are exposed to combinations of heat, irradiation, stress and corrosion for extended periods of time is also needed. An essential part of that understanding has come from studies at the atomic scale, following the development of high-resolution experimental techniques such as small angle neutron scattering (SANS), atom-probe tomography (APT), and transmission electron microscopy (TEM). Atom-probe tomography has benefited from remarkable technical advances in the last decade with the development of faster voltage pulsers, larger detectors (and therefore a wider field of view) and shorter laser pulses with faster repetition rates 8 . These developments have allowed significantly more efficient data collection and opened atom-probe tomography analysis to brittle microstructures such as oxide/metal interfaces and less conductive materials 9,10 . Moreover, progress in focused ion beam (FIB) technology 11,12 has also permitted the development of novel sample preparation techniques 13 and analysis of samples containing pre-selected features 14,15 . Electron microscopy has also seen significant developments. With the advent of aberration correctors 16 , high resolution electron energy loss spectroscopy (EELS) 17 , energy filtered transmission electron microscopy (EFTEM), and advanced data analysis approaches such as multivariate statistical analyses 18 to improve signal/noise ratio 19 have extended analytical TEM approaches to much smaller features than previously possible. Moreover electron tomography 20 and confocal microscopy 21,22 have now enable electron microscopy to provide three-dimensional imaging.

Considerable progress is now being made towards an atomistic understanding of materials degradation. This article provides a series of examples on how the above described state-of the art techniques may be applied, focusing first on irradiation-induced or accelerated precipitation in steels and W alloys, followed by some development on corrosion studies in Zr alloys and stress corrosion cracking in steels. Recent results on oxide-dispersion strengthened steels are then presented to demonstrate how atomic-scale characterization can provide a unique feedback into the development of new alloys. Some outstanding challenges and future directions for research are also identified.

Irradiation-induced embrittlement

Irradiation-induced accelerated ageing is a crucial issue that limits the lifetime of nuclear reactors. The phenomenon of irradiation-induced or -enhanced precipitation has been studied in many model systems using conventional TEM methods and this work has been reviewed by Russell 23 . Continued scrutiny of actual surveillance samples and candidate materials irradiated in test reactors is necessary to aid the prediction of microstructural changes, and consequent potential changes in structural integrity, of materials used in service. Extensive research on ferritic steels used to manufacture reactor pressure vessels (RPVs) has demonstrated that irradiation-induced damage can be classified as a combination of matrix damage resulting from radiation produced point defect clusters, the radiation-enhanced formation of 1–2 nm diameter clusters containing solutes such as Cu, Mn, Ni and Si and the radiation-enhanced segregation of elements

(a) (b)
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Fig. 1 (a) 3D atom-probe tomography reconstruction of an irradiated RPV steel. Each dot represents an individual atom in a volume of ~90x90x380 nm 3 . The left hand image shows the location of carbon atoms and the right hand image the location of Cu atoms. A grain boundary, a large Cu precipitate, two carbides, several dislocations and several hundred small Cu-enriched clusters can be identified; (b) Enlarged view of a single irradiation-induced cluster (extents of outline box 8x8x8 nm 3 ).

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of a single irradiation-induced cluster (extents of outline box 8x8x8 nm 3 ). NOVEMBER 2009 |

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such as P to grain boundaries 24-26 . Despite the very small size of the irradiation-induced clusters, they can have a dramatic and deleterious effect on materials properties 27 . The irradiation-induced clusters act as barriers to dislocation movement resulting in an increase in hardness leading to embrittlement. Irradiation-induced segregation of

P to grain boundaries can lead to non-hardening embrittlement, by

reducing the energy required to propagate an intergranular fracture. Using microstructural information to develop an improved mechanistic understanding of RPV embrittlement contributes to the safety cases for commercial RPVs. For instance, APT can be used to study the early stages of precipitation. This is an area of increasing interest on two counts: 1) the mechanisms of cluster formation are poorly understood, and 2) modelling has predicted the formation late blooming phases (LBPs) in RPV steels containing relatively high Ni 28 . The latter issue

is an increasing concern as plant operators are looking to extend

plant life beyond the original design life of the RPV. There is a need to ensure methodologies are in place to detect the early stages of LBPs. A significant amount of work in a number of laboratories has been dedicated to characterizing these small clusters using electron

microscopy 29 , small angle neutron scattering 30,31 , and atom-probe tomography 32-37 as well as modelling 38 . APT data obtained from

an irradiated RPV steel is presented in Fig. 1. Fig. 1a illustrates the complex distribution of small (1-2 nm diameter) irradiation-induced clusters, some of which are spatially correlated with dislocations and some found within the matrix. In addition larger precipitates (>10 nm diameter) such as carbides and fcc Cu are also observed. Many of these will have formed during the fabrication of the weld or during the post-weld heat treatment. The figure also shows the presence of a grain boundary that is enriched in C (as shown) and also elements such as P (not shown). Fig. 1b shows a highly magnified view of a single irradiation-induced cluster containing Cu, Mn, Ni and Si atoms. The

P atoms tend to be found at peripheries of the clusters. This example

demonstrates how microstructural characterization, using techniques such as atom-probe tomography, is imperative because it underpins the mechanistic understanding of the damage processes and can therefore help provide confidence when predicting materials properties at higher doses or in materials of different composition. Another example of precipitation under irradiation relates to W alloys to be used as plasma facing components in fusion reactors 39 . Neutron irradiation induces significant transmutation of W into Re and Os 39,40 . Precipitation of these alloying elements could dramatically modify the properties of the initial material. Using atom-probe tomography, Seidman et al. 41,42 showed that neutron irradiation could trigger the precipitation of nanoscale precipitates of the σ and χ phases in W-10 and 25 at.%Re alloy irradiated between 575 and 675 °C to 8.6 dpa. More observations of precipitation in irradiated W alloys have been made since 43-47 and more recent atom-probe tomography observations of W-implanted W-Re alloys revealed the onset of phase separation at low doses. Fig. 2 shows 3D reconstruction of a W-25

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(a) (b)
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Fig. 2 5 nm thick slices through atom-probe tomography reconstructions obtained from a W-25at.%Re alloy. Only Re atoms are shown. (a) Re is in solid solution before implantation (a) and (b) clustered after implantation by 2MeV W ions at 500 °C to 2.8 dpa. (b) The concentration distributions confirm the random Re distribution before implantation and non-random one after implantation.

at.%Re alloy before and after implantation revealing the formation of nanometer-scale Re-rich clusters after only 2.8 dpa at 500 °C. Our understanding of irradiation-induced precipitation in W alloys is still inadequate, in great part due to the lack of knowledge of the phase diagram. While the high temperature part of the W-Re phase diagram predicts complete solid-solution up to 22 at.%Re, the lower part of the diagram (T<1500 °C) cannot be assessed experimentally for kinetic reasons 48 and therefore relies on Calphad predictions 49 . Systematic atomic-scale experimental and theoretical work 50 may pave the way towards a better understanding. A more recent issue involves the stability under irradiation of Fe-Cr based alloys, in particular Fe-7-18 at.%Cr alloys that form the basis for oxide dispersion strengthened (ODS) ferritic steels, a promising class of structural material for nuclear applications. They have the advantage of low swelling characteristics compared with the austenitic stainless steels and adequate mechanical properties. Ferritic Fe-Cr alloys, however, have the disadvantage of possible α ’ precipitation under irradiation that would cause loss of ductility 51 and corrosion resistance 52 . The ability to predict microstructural stability and understand irradiation effects starts with thermodynamic phase diagrams. The case of the Fe-Cr system is interesting since the conventional low temperature phase diagram 53 following Calphad calculations 54 is erroneous. The magnetic frustration in this system leads to a negative heat of mixing at low concentrations and the recalculated phase diagrams, based on density functional theory calculations, predict a maximum solubility of Cr in Fe of between 6 and 9 at.%Cr at room temperature 55-60 . Whether precipitation under irradiation is accelerated 61,62 , induced 63,64 or occurs by

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different mechanisms depending on Cr concentration 65 remains an open question that would strongly benefit from further atomic-scale analyses. Knowledge of thermodynamic properties, solute/defect interactions and diffusional paths are important elements to support informed predictions for reactor lifetime and provide solutions to retard materials degradation. As illustrated in the previous selected examples, atomic scale analyses in combination with atomistic modelling provide a unique approach towards solving some of the problems outlined above.

Corrosion resistance

Degradation of materials involving corrosion and environmentally assisted cracking (EAC) are significant issues for nuclear power plants. Stress corrosion cracking (SCC) in particular is a major concern in both pressurised water reactors (PWR) 66 and boiling water reactors (BWR) 67 and has cost billions of dollars to the nuclear industry in repair, inspection and replacements. SCC of cold-worked austenitic steels has recently been reported in operating PWR plants 68 as predicted by autoclave testing 69 . Although crack initiation and propagation usually take place in three dimensions, conventional characterization techniques are typically restricted to two dimensional observations. This has made the interpretation of cracking phenomena a very challenging task. Cold worked stainless steels, in particular, present an extremely complex interaction between the microstructure, stress and environment which can benefit from

3D microstructural observations at, or near, the atomic scale. FIB 3D slicing 70 , electron tomography and atom probe tomography have already been applied 71 . Such characterizations of SCC crack tips have proven to be an excellent tool for accurately measuring crack opening, understanding 3D crack morphology and visualizing atomic- scale crystallographic features, such as sub-boundaries, deformation bands and oxides. As shown in Fig. 3a, 3D FIB slicing has revealed how accelerated oxidation takes place along the twin deformation bands (TDBs) that intersect the crack flanks. In Fig. 3b and 3c, atom-probe tomography was used to illustrate the complex surface oxidation processes that take place in cold-worked stainless steels. The reconstruction was taken from a sample tested in an autoclave under PWR primary water conditions for 1500 h. It developed a Cr-rich oxide layer of around ~200 nm in thickness and analysis of the 3D chemistry below the cap oxide also revealed significant and complex oxidation of sub-surface features. The influence of these features on the corrosion properties of the steel is not well understood. Further 3D analyses of suitable SCC materials at, or near, the atomic scale should provide insight into the mechanisms of SCC and will help the development and validation of accurate, predictive models. Zr alloys are currently heavily used as fuel cladding materials but their corrosion rate limits the operating lifetime of the fuel assemblies. Alloying has turned out to provide a significant improvement to the corrosion resistance, but an empirical approach is still taken for the selection of alloying additions 72 . Solving corrosion issues, including preventing the breakaway regime 73 , where the protective nature of the

(a) (b) (c)
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Fig. 3 (a) Reconstructed volume from a collection of FIB sliced images showing an open crack (blue) and oxidized TDBs (green), in a 304SS with 20 % cold-work oxidized under simulated PWR primary water (b) Atom-probe reconstruction of a near-surface region showing the distribution of Cr and Fe atoms within oxides. Complex patterns of oxidation are revealed by the distribution of Cr- and Fe- oxides (green-blue dots) and surfaces of approximately 10 % oxide concentration (green). The dashed line (black) indicates the location of the oxide-metal interface. The vertical cylinder shows the region from which the 1D concentration profile shown in (c) was generated. In (c), all complex ions are decomposed into atomic species. The left side of the profile corresponds to the surface oxides with Li incorporated in the oxide after exposure to primary water. The O-rich region on the right side is a sub-surface oxidized feature 71 .

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(a)

(b)
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Fig. 4 (a) Atom-probe tomography reconstruction of the metal/oxide interface of pre-transition Zircaloy-4 specimens oxidised in 360 ºC primary water. The reconstruction displays Zr (green), ZrO (blue), O 2 (orange) and Fe (red) ions. The metal/oxide interface is normal to the analysis direction. Iron is seen to be segregated to the Zr/ZrO boundary. This material is rejected from the sub-oxide during the progression of the oxide front into the metal. (b) 1D concentration profile across metal/oxide interface reveals an intermediate ZrO oxide phase.

oxide layer suddenly fails and corrosion progresses at a significantly greater rate, is crucial if Zr alloys are to be used in high fuel burn-up scenarios. A full mechanistic understanding of the processes that occur at the metal/oxide interface is required for the control of oxidation kinetics. Once again, atomic-scale characterization offers the possibility of a new insight into old outstanding issues. Past investigations using surface analysis techniques 74 have indicated the possible existence of a sub- stoichiometric oxide layer between the metal and ZrO 2 during the initial oxidation of zirconium. A number of TEM studies have also been carried out on various zirconium alloys to investigate the nature of such an oxide

layer, e.g. 75,76 , resulting in considerable disagreement on the structure and composition of the oxide/metal interface. Atom-probe tomography analyses of the metal/oxide interface (Fig. 4) have revealed that the composition of the intermediate layer is that of ZrO, while the ceramic oxide is ZrO 2 . The oxygen content in the metal adjacent to the interface appears high and corresponds to the limit of solubility for O in Zr. As illustrated by the above two examples, three-dimensional imaging coupled with atomic-scale analysis are revolutionizing our understanding of oxide formation during surface oxidation as well as environmentally assisted cracking.

(a) (b)
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Fig. 5 Grain boundary chemistry in an ODS Fe-12wt.%Cr alloy measured by APT (a) and EELS (b); The APT 1D profile across the grain boundary and the EELS profile along the red line reveal similar Cr segregation levels at these two grain boundaries. (Material courtesy of Prof. Pareja, Universidad Carlos III de Madrid).

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Solute/defect interactions

Understanding microstructural evolution under irradiation requires the detailed knowledge of defect formation, mobility and interactions with solute atoms. Irradiated microstructures have been extensively studied for the last forty years. Defect formation, mobility, and dislocation structures in particular have been described in many materials systems under different types of irradiation (e.g. 77 ). More recently, Jenkins et al. 78,79 have revisited the issue of loop formation in Fe and Fe-Cr alloys during in-situ Fe ion irradiation, and in conjunction with theoretical modelling were able to describe in detail the formation and development of geometrical loop patterns as a function of irradiation temperatures. Under irradiation conditions, interactions between solute atoms and point defects (vacancies and interstitials) can cause coupled transport of solute atoms by point defect fluxes, giving rise to non-equilibrium segregation phenomena 80,81 , first postulated by Anthony 82 and observed by Okamoto and Weidersich 83,84 . The segregation of alloying elements towards or away from dislocations, grain boundaries and other types of defects has been observed in a wide range of irradiated structures (e.g. 85-89 ), and a great deal of experimental and theoretical research has been directed towards developing a basic understanding of this phenomenon. Solute segregation will not only influence the surface-composition- sensitive phenomena such as corrosion, and preferential sputtering, but will also affect bulk properties such as void swelling and phase instabilities 90 . The technological impact of irradiation-induced solute segregation or depletion should be of serious concern, and has yet to be fully understood 91 . In particular, grain boundary orientation, alloy composition and the role of impurities need to be clarified. Atomic- scale studies already provide valuable information as illustrated in Fig. 5 with the analysis of Cr segregation at grain boundaries in oxide dispersion strengthened steels.

Oxide dispersion strengthened steels

In the search for structural materials capable of higher operating temperatures while resistant to high neutron fluxes, oxide dispersion strengthened alloys have emerged as the most promising candidates. The particular need for limited swelling, limited residual radioactivity, good corrosion resistance, have narrowed the search to ODS ferritic Fe-9-14at.%Cr steels. These are produced by ball milling, using Y 2 O 3 powder mixed to a base composition powder, followed by either hot extrusion or hot isostatic pressing. The resulting microstructure can be complex with sub-micron sized grains and a very fine distribution of nanoscale oxide particles that contributes to the improved high temperature strength properties 92 . The nanoscale particles also improve resistance to irradiation by providing a high density of trapping sites 93 . Optimizing properties and microstructure is an on-going task that requires careful control over the precipitate size, number density, interfacial properties, etc. Yet the exact nature of the oxide particles is still unclear and the terminology (particles, precipitates, clusters, nano-

(a) (b)
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Fig. 6 (a) TEM and APT reconstruction of ODS Eurfer97 steel showing the presence of larger particles along a grain boundary than within grains (material courtesy of Dr. Lindau, FZK); (b) 3D reconstruction from an ODS Fe-12wt.%Cr alloy showing the inhomogeneous distribution of particles (material courtesy of Prof. Pareja, Universidad Carlos III de Madrid).

clusters, nanofeatures, etc.) confused. The mechanisms and kinetics by which these clusters form, their structure, composition, and interface character need elucidating and the nanoscale character of the features requires atomic-scale characterization. Atom-probe tomography analysis of oxide particles was first performed by Larson et al. who revealed 1-2nm Y and O-rich features in a 12YWT alloy 94 . Following this work, Miller et al. characterized several ODS steels focusing on the composition of the nanoscale features, revealing high Fe concentrations 95,96 , partitioning of Ti when present in the steel 95,97 , and strong resistance to coarsening at temperatures as high as 1400 °C 98 . The three-dimensional approach to characterization has allowed quantification of composition and size distribution. It has revealed the presence of larger particles at grain boundaries, as illustrated in 99 and in Fig. 6a, thereby suggesting a strong role of defects in the kinetics of growth. It has also shown the difficulty in realizing perfectly homogeneous materials as illustrated in Fig. 6b. Determining the compositions of the oxide clusters is particularly challenging because of the small sizes. The amount of Fe for instance found in the clusters depends strongly on alloy composition, processing routes, experimental conditions, and analysis methods (small angle neutron scattering, TEM, or APT) as reviewed in 93 . Atomic-scale methods have, however, revealed a core/shell structure (Fig. 7) 100,101 in different ODS alloys of different compositions. The non- stochiometric compositions measured experimentally suggest that the oxide particles may be nucleating with a metastable structure and theoretical calculations have started to tackle this question. Fu et al. 102 suggested that vacancy/solute interactions promote the nucleation

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(a) (b)
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Fig. 7 Core/shell structure of nanoscale oxide particles in an ODS Fe-12 wt.%Cr alloy as revealed by EFTEM and APT. (a) EFTEM elemental maps were extracted from a dataset reconstructed with multivariate statistical analysis 101 . A line profile across the biggest precipitate reveals a Cr-rich shell of around 2 nm width. (b) APT reconstruction of a particle exhibiting a Cr rich shell (blue dots) around a Y-rich core. The 1D profile across the particle confirms the presence of Cr at the matrix/oxide interface 100 . (material courtesy of Prof. Pareja, Universidad Carlos III de Madrid).

of non-stochiometric phases and positron annihilation spectroscopy experiments appeared to confirm this 103 . It is only by closely combining atomic-scale experiments with theoretical calculations that the exact nature of the oxide nanoclusters, their stability and the role of vacancies will be elucidated.

Conclusions

While most of the issues outlined in this article have yet to be solved, atomic-scale characterization has a vital role to play in ensuring the safety and integrity of the power plants that are needed to provide the world with reliable, 24-hour per day base load capacity for electricity generation, with ultra-low carbon emissions. The issues associated with material degradation in a nuclear reactor environment continue to push the limits of available experimental techniques but fast progress has already been achieved with high-resolution analytical

TEM and APT approaches. Although not discussed in this article, other techniques, such as small angle x-ray and neutron scattering or positron annihilation spectroscopy, are also essential for a complete understanding of materials. Future developments should include small scale testing of selected materials features in combination with atomic-scale characterization as well as atomistic modelling to provide a full description of defect behaviour under irradiation, heat, stress and

corrosion conditions.

under irradiation, heat, stress and corrosion conditions. Acknowledgements EAM acknowledges the UK Royal Society for

Acknowledgements

EAM acknowledges the UK Royal Society for funding; SL-P acknowledges INSS (Japan) for support. All APT analyses were conducted within the UK atom probe facility (Opal) at the University of Oxford, funded by the U.K. Engineering and Physical Sciences Research Council (EPSRC) under grant

EP/077664/1.

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