www.materialstoday.

com NOVEMBER 2009 | VOLUME 12 | NUMBER 11

Energy uncovered
Reactor design and modelling, the new blue print

Available online at

www.sciencedirect.com
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 EDITORIAL

Energy crisis
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NOVEMBER 2009 | VOLUME 12 | NUMBER 11 1

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 www.materialstoday.com CONTENTS

Contents
Regulars
Editorial 1
Energy crisis
Can fusion and fission harness a new hope for our energy needs?

Comment | Bruce Mendelsohn 6

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

Research News 8
Pencilled in: graphite’s ferromagnetism | Magnetricity: The new
magnetic electricity | New nano-sensor speeds up DNA detection | 8 Magnetic moments captured in graphitic defects
Butterfly wings inspire new research | Small and powerful nuclear battery
developed | Every silver-lined solar cell | Origami tubes

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
9 Butterfly wing replica
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
10 Typical polymer solar cell material
Lalko, Pratik Chhetri, Bard Fahlman and Anja Mueller, Central Michigan University.

NOVEMBER 2009 | VOLUME 12 | NUMBER 11 3

CONTENTS www.materialstoday.com

Lead story 12 Next issue

Structural materials for fission & fusion Materials Today will
energy feature the current state
In many cases, a key strategy for designing high-performance of play in the fascinating
radiation-resistant materials is based on the introduction of a world of metamaterials,
high, uniform density of nanoscale particles that simultaneously current research trends,
provide good high temperature strength and neutron radiation applications and future
damage resistance. direction.
Steven J. Zinkle and Jeremy T. Busby Optical nano-
antennas and
metamaterials
Energy uncovered A review of some of the recent
approaches to transmission
enhancement and light harvesting.
Review 20
Anisotropic
Discovery and design of nuclear fuels
metalmaterial
Multi-scale models and simulations are used to predict
irradiation effects on properties such as thermal conductivity, devices
oxygen diffusivity, and thermal expansion. Recent progress on the parametric
design of transformation devices
Marius Stan
is covered in this review article.
Review 30 Phononic crystals
Nuclear reactor materials at the atomic scale and acoustic
With the renewed interest in nuclear energy, developing new
materials able to respond to the requirements of the next-
metamaterials
Current research and trends in
generation fission and future fusion reactors becomes a priority.
phononic crystals are covered in
Emmanuelle A. Marquis, Jonathan M. Hyde, David W. Saxey, Sergio
this paper.
Lozano-Perez, Vanessa de Castro, Daniel Hudson,
Ceri A. Williams, Samuel Humphry-Baker and George D.W. Smith
Electromagnetic
Review 38 wave in 2D
photonic crystals
Modeling plasma facing materials for fusion power Progress on the negative
Duffy describes the methods used for modeling the response of refraction and the abnormal
plasma facing materials to the conditions experienced in a fusion transmission of electromagnetic
reactor.
waves in 2D photonic crystals is
D. M. Duffy covered in this paper

Review 46 Resonance
Multiscale Modelling: the role of helium in iron properties of
This review discusses the modelling paradigms used to investigate metallic ring
and obtain an understanding of the mechanisms at play in helium
systems
bubble nucleation and growth in ferritic steels.
A rigorous mode-expansion
Maria Samaras theory is proposed to help
understand resonance properties
Review 54 of metallic ring systems.
Neutron scattering and hydrogen storage
Hydrogen has the largest scattering interaction with neutrons of Mie resonance-
all the elements in the periodic table making neutron scattering based dielectric
ideal for studying hydrogen storage materials. metamaterials
A. J. Ramirez-Cuesta, M. O. Jones and W. I. F. David Novel applications are
discussed in this paper

4 NOVEMBER 2009 | VOLUME 12 | NUMBER 11

 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
BUDDY D. RATNER practice of biomaterials.
2009
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.

www.elsevier.com/locate/actabiomat
COMMENT
Transforming Engineers into Engineering Leaders
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
6 NOVEMBER 2009 | VOLUME 12 | NUMBER 11
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/.
 In partnership with

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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
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
8 NOVEMBER 2009 | VOLUME 12 | NUMBER 11
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
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
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
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

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”
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.
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
features make it very suitable for cost-effective
mass production. According to Dr. Gao, the new
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
NOVEMBER 2009 | VOLUME 12 | NUMBER 11
RESEARCH NEWS
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:
www.ibn.a-star.edu.sg
Elisabeth Lutanie
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
9
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
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.
10 NOVEMBER 2009 | VOLUME 12 | NUMBER 11
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
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
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
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
 RESEARCH NEWS

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
(a)
(b)
DNA origami
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
(c)
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, 4th sentence from the bottom of column 2,
“crystalline” should be replaced with “thin”. On page 24, 5th line down first column,
reference 5 should follow “Song et al”. On page 29, 8th 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, 4th 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 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 reactors1,2, along with advances in the
plasma physics knowledge required for heating and controlling
fusion energy reactions3-5, 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 electricity6. The vast majority of
these reactors are based on uranium dioxide fuel pellets arranged in
long cylinders (“fuel rods”) with surrounding flowing water channels.

12 NOVEMBER 2009 | VOLUME 12 | NUMBER 11 ISSN:1369 7021 © Elsevier Ltd 2009

 Structural materials for fission & fusion energy
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 reactors8.
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/m2 (~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 UO2 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
Fig. 1 Schematic of key components utilizing structural materials in pressurized water fission reactor8.
REVIEW
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
NOVEMBER 2009 | VOLUME 12 | NUMBER 11 13
REVIEW 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 operating9,10. 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
cracking11, 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 unpredictability12. 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-confined4,13,14 and inertially-confined13,15,16
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 reactor5 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
14 NOVEMBER 2009 | VOLUME 12 | NUMBER 11
Fig. 2 Schematic of key components in a magnetically-confined fusion reactor,
based on the ARIES-AT tokamak reactor design study5.
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
considerations19,20.
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 corrosion19,21-31. 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/m2,
which is substantially higher than the highest heat flux for structural
materials in fission reactors (~1 MW/m2 for the fuel cladding). The
Table 1. Summary of leading proposed structural
materials, coolant and tritium generation concepts
for fusion energy systems19,20. The filled cells in the
table indicate material combinations that are under
consideration for fusion energy blankets. FLiBe is a LiF-
BeF2 molten salt.
Coolant/Tritium Generating Material System
Structural
Material H2O/ He/Li H2O/Li FLiBe/
Li/Li He/PbLi
PbLi ceramic ceramic FLiBe
Ferritic steel
V alloy
SiC/SiC
 Structural materials for fission & fusion energy
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 structures21,23,26,29,32-35. Consideration of this reduced-
activation mandate, along with the requirement for high performance,
leads to three major options for fusion structural materials21. 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
option21,36-41, 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 resolved39,40,42-46. Refractory alloys based on
either vanadium47-50 or tungsten30,51-53 alloys represent a higher
performance, higher risk option. Vanadium alloys are particular
attractive for self-cooled lithium blanket systems19, but are not
considered to be viable for other blanket concepts21. 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
applications21. 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
potential54-57.
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
quantified58-61 in terms of displacements per atom, dpa. A damage
level of 1 dpa corresponds to “stable” displacement of every atom
REVIEW
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 value58,60,61 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 levels60,62. These phenomena are summarized in Fig. 3.
At low temperatures (below 0.3-0.4 TM, where TM 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
Fig. 3 Summary of five radiation damage threats to structural materials
performance.
NOVEMBER 2009 | VOLUME 12 | NUMBER 11 15
REVIEW Structural materials for fission & fusion energy
centered cubic metals and alloys63. 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 TM) that can lead to
localized corrosion or mechanical property degradation such as grain
boundary embrittlement64, void swelling from vacancy accumulation
(0.3-0.6 TM) that can create unacceptable volumetric expansion65, and
radiation induced creep65 and/or anisotropic growth66 (0.2-0.6 TM)
that can produce dimensional expansion along directions of high stress
and/or specific crystallographic directions. At very high temperatures
(>0.5 TM) 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 materials67. 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
states68. 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
16 NOVEMBER 2009 | VOLUME 12 | NUMBER 11
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 transients69. 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
effects69.
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 subcomponents9. 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 ~1022 n/cm2 and ~1023 n/cm2 (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 levels24,65,68,
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
operation70.
 Structural materials for fission & fusion energy
In addition to elevated temperatures, intense neutron fields, and
stress, components must also be able to withstand a corrosive aqueous
environment71. 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 applications24,27,72-77. 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 compatibility78 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.
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).
REVIEW
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
environment30,79, 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 used80. 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
years87. Materials science tools such as computational thermodynamics
and multiscale radiation damage computational models, in conjunction
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 17
REVIEW Structural materials for fission & fusion energy
Fig. 6 Historical rate of improvement in the maximum operating temperature
for four generations of structural steels, based on results summarized by
Viswanathan87.
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
tools37,41,81-84,86,88-90. For example, first principles atomistic modeling
results91 provided important insight that the formation of highly stable
nanoscale clusters enriched in Y, Ti and O from initial Y2O3 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 steel44,92. 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)2C precipitates93. Fig. 7 compares the
fracture toughness versus tensile strength behavior for the Aermet
precipitation-strengthened steel93 and the 14YWT nanocluster-
strengthened steel92 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)2C
strengthened steels.
18 NOVEMBER 2009 | VOLUME 12 | NUMBER 11
Fig. 7 Tradeoff between fracture toughness and tensile strength for
conventional and advanced92,93 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 strength94, 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
resistance86. 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
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.
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Acknowledgments
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Research and Development program, Office of Nuclear Energy and by the
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NOVEMBER 2009 | VOLUME 12 | NUMBER 11 19
 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 UO2 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
fuels requires a strict control of composition, thermal treatment,
pressure, and atmosphere1-3. 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 rods4,5. Once in the reactor, the fuels
and structural materials (pressure vessels, pipes, ducts, etc.) are
subjected to radiation environments that continuously alter their

20 NOVEMBER 2009 | VOLUME 12 | NUMBER 11 ISSN:1369 7021 © Elsevier Ltd 2009

 Discovery and design of nuclear fuels
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 in15. The scientific
method of investigating natural phenomena (recently under serious and
loving scrutiny16) 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.
thermo-mechanical properties6-10. It is well documented11 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
bubbles12-14 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
clusters19-27, chemical species and fission-product migration28-31, gas
bubbles formation32, thermal conductivity33-35, oxygen diffusivity36,37,
dislocations38-41, thermal expansion42, and phase stability/
transformations43,44. One of the most challenging aspects is modeling
the complex electronic structure of materials in general45, and the
actinides (especially Pu) in particular46,47 as well as the stability of their
phases48. Another challenge is modeling high temperature effects such
as entropic contributions to the free energy of liquids49.
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 continuum55.
REVIEW
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 (see17 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 (see18 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.
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 oxides19 and
plutonium oxides56. Several models include the dependence of the
properties on the oxygen content. Building on thermochemical
studies57-59, 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 fuel60.
NOVEMBER 2009 | VOLUME 12 | NUMBER 11 21
REVIEW Discovery and design of nuclear fuels
Box 2.
Multi-scale models and simulations
This section builds upon a recent discussion of modern epistemic
concepts42. 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 validation50. Verification is the process by which the fidelity of a
numerical algorithm with respect to underlying mathematical
Fig. 2 Multi-scale theoretical and computational methods used for materials model development and computer simulations.
Fig. 3 shows a comparison of experimental61 and simulation62 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 PuO2 fuels56,63,64. Although
not as extensive, the work on other ceramic fuels such as nitrides65,66
22 NOVEMBER 2009 | VOLUME 12 | NUMBER 11
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 approach42,51-53. The
information is transferred between scales via characteristic parameters
such as density, energy, temperature, or grain size distribution54. 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.
or carbides (with application to coated particle fuels67,68), as well as
studies of surrogate materials based on cerium69 or dysprosium66 are
most encouraging.
Fuel performance (see Box 3) is another area that has benefited
from advanced models and simulations70. Understanding complex
phenomena in fuel elements provides important input to reactor
simulations, currently based on homogenization techniques77. Recent
studies have examined in more detail the thermochemistry of the
 Discovery and design of nuclear fuels
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 operation71,72. 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 proposed42. 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 models65,70. Other requirements are related to
numerical algorithm design, uncertainty quantification, and software
engineering, including
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.
REVIEW
the use of nested (linear + non-linear) solvers74,75, 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 processes76.
fuel-clad interactions78,79 and the influence of temperature and fuel
stoichiometry changes on the coupling of heat and species transport in
a UO2 fuel element with stainless steel clad80. 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 expansion81, 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 (1012 operations per second) and the number of
petaflop (1015 operations per second) supercomputers is increasing
NOVEMBER 2009 | VOLUME 12 | NUMBER 11 23
REVIEW Discovery and design of nuclear fuels

Fig 4. Simulation of heat transport in a UO2+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 pace82. Already, neutron diffusion calculations, as well as
some reactor hydrodynamics simulations83,84 are being performed on
such resources. As exaflop computers (1018 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 ideas85. 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.

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

24 NOVEMBER 2009 | VOLUME 12 | NUMBER 11

 Discovery and design of nuclear fuels
• Atomistic (e.g. Molecular Dynamics) simulations of a much larger
number of atoms (1020), compared to the current state of the art
(108). 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
cracking86.
• 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
Fig. 6 Schematic representation of the main components of an Institute for
Materials Discovery and Design (IMDD).
REVIEW
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 reactors87-91. 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 (ThO2 based
fuels are already here92), Am (already in some mixed oxide fuels93),
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.
NOVEMBER 2009 | VOLUME 12 | NUMBER 11 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 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
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 fuels94) and nuclear energy
in general95. 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.
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REVIEW
Summary and outlook
New generation, innovative nuclear fuels will be complex, multi-
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Self-assembly has been likened to taking a jigsaw puzzle box, shaking it and when you open the box you find the jigsaw puzzle
correctly made! As research in this field develops, we are continually finding more and more naturally occurring self-assembly systems
in the complex world around us.
The breadth of application of self-assembly vast and this educational webinar will focus on:
➜ Using Self-Assembled Monolayers and Mass Spectrometry for BioChip Applications
➜ Self and Directed Assembly for the Control of Single Molecule Environments
The webinar is aimed at alternative energy researchers, surface chemists, mass spec audience, organic electronics, polymer science, self-
assembly, molecular electronics and a number of biological audiences such as: proteomics, enzyme researchers and analytics.

Registration Details:

➜ www.materialstoday.com/webinars
 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. Marquis1*, Jonathan M. Hyde1,2, David W. Saxey1, Sergio Lozano-Perez1, Vanessa de Castro1, Daniel Hudson1,
Ceri A. Williams1, Samuel Humphry-Baker1 and George D.W. Smith1
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 production1. In the longer term, fusion energy
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 ITER2 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 20403. 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

30 NOVEMBER 2009 | VOLUME 12 | NUMBER 11 ISSN:1369 7021 © Elsevier Ltd 2009

 Nuclear reactor materials at the atomic scale
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 weldability4-6. It is anticipated that the blanket
structures of DEMO, will have to sustain doses of the order of >50dpa/
year7, 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
design6 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 rates8. 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 materials9,10. Moreover,
progress in focused ion beam (FIB) technology11,12 has also permitted
the development of novel sample preparation techniques13 and analysis
of samples containing pre-selected features14,15. Electron microscopy
has also seen significant developments. With the advent of aberration
correctors16, high resolution electron energy loss spectroscopy
(EELS)17, energy filtered transmission electron microscopy (EFTEM),
and advanced data analysis approaches such as multivariate statistical
analyses18 to improve signal/noise ratio19 have extended analytical
TEM approaches to much smaller features than previously possible.
Moreover electron tomography20 and confocal microscopy21,22 have
now enable electron microscopy to provide three-dimensional imaging.
REVIEW
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 Russell23. 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)
Fig. 1 (a) 3D atom-probe tomography reconstruction of an irradiated RPV
steel. Each dot represents an individual atom in a volume of ~90x90x380 nm3.
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 nm3).
NOVEMBER 2009 | VOLUME 12 | NUMBER 11 31
REVIEW Nuclear reactor materials at the atomic scale
such as P to grain boundaries24-26. Despite the very small size of the
irradiation-induced clusters, they can have a dramatic and deleterious
effect on materials properties27. 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 Ni28. 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
microscopy29, small angle neutron scattering30,31, and atom-probe
tomography32-37 as well as modelling38. 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 reactors39.
Neutron irradiation induces significant transmutation of W into Re and
Os39,40. 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 since43-47 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
32 NOVEMBER 2009 | VOLUME 12 | NUMBER 11
(a) (b)
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
reasons48 and therefore relies on Calphad predictions49. Systematic
atomic-scale experimental and theoretical work50 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 ductility51
and corrosion resistance52. 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 diagram53 following Calphad
calculations54 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 temperature55-60. Whether precipitation
under irradiation is accelerated61,62, induced63,64 or occurs by
 Nuclear reactor materials at the atomic scale REVIEW

different mechanisms depending on Cr concentration65 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 plants68 as predicted by autoclave testing69. 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
slicing70, electron tomography and atom probe tomography have
already been applied71. 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 additions72. Solving corrosion issues, including
preventing the breakaway regime73, where the protective nature of the

(a)

(b) (c)

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 feature71.

NOVEMBER 2009 | VOLUME 12 | NUMBER 11 33

REVIEW Nuclear reactor materials at the atomic scale

(a) (b)

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), O2 (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 techniques74 have indicated the possible existence of a sub-
stoichiometric oxide layer between the metal and ZrO2 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 ZrO2. 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)

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).

34 NOVEMBER 2009 | VOLUME 12 | NUMBER 11

 Nuclear reactor materials at the atomic scale
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 phenomena80,81, first postulated by
Anthony82 and observed by Okamoto and Weidersich83,84. 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
instabilities90. The technological impact of irradiation-induced solute
segregation or depletion should be of serious concern, and has yet to
be fully understood91. 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 Y2O3
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 properties92. The nanoscale particles also improve
resistance to irradiation by providing a high density of trapping sites93.
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-
REVIEW
(a) (b)
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 alloy94. Following this work, Miller et al. characterized
several ODS steels focusing on the composition of the nanoscale
features, revealing high Fe concentrations95,96, partitioning of Ti
when present in the steel95,97, and strong resistance to coarsening at
temperatures as high as 1400 °C98. 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 in99 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 in93. 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
NOVEMBER 2009 | VOLUME 12 | NUMBER 11 35
REVIEW Nuclear reactor materials at the atomic scale

(a) (b)

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 analysis101. 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 interface100. (material courtesy of Prof. Pareja, Universidad Carlos III de Madrid).

of non-stochiometric phases and positron annihilation spectroscopy
experiments appeared to confirm this103. 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.
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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NOVEMBER 2009 | VOLUME 12 | NUMBER 11 37
 Modeling plasma facing
materials for fusion power
Plasma facing materials, the materials that line the vacuum vessel,
experience particularly hostile conditions as they are subjected to high
particle and neutron flux and high heat loads. Plasma facing materials
must have high thermal conductivity for efficient heat transport, high
cohesive energy for low erosion by particle bombardment and low atomic
number to minimize plasma cooling. These contradictory requirements
make the development of plasma facing materials one of the greatest
challenges ever faced by materials scientists. Modeling has made, and
continues to make, a valuable contribution to the understanding of the
various processes involved in the radiation damage of plasma facing
materials. The techniques used to model the effects of high thermal
and particle flux range from ab initio techniques that study processes
occurring on femtosecond timescales and nanometre length scales,
to molecular dynamics for intermediate length and timescales and
finite element models for macroscopic length scales and experimental
timescales. The synergy between the effects of the plasma, high heat
flux and particle flux presents particular challenges for modeling. In
this review we summarise the potential candidates for plasma facing
materials and describe the methods used for modeling the response of
these materials to the conditions experienced in a fusion reactor.
D. M. Duffy
London Centre for Nanotechnology and Dept. of Physics and Astronomy, University College London, Gower Street, London, WC1E 6BT, UK
EURATOM/CCFE Fusion association, Culham Science Centre, Oxfordshire, OX14 3DB, UK
Email: d.duffy@ucl.ac.uk

38 NOVEMBER 2009 | VOLUME 12 | NUMBER 11 ISSN:1369 7021 © Elsevier Ltd 2009

 Modeling plasma facing materials for fusion power REVIEW

The successful commercialisation of fusion power would offer a Plasma facing materials
safe, carbon free solution to the world’s energy supply problem1 The materials that line the vacuum vessel are subjected to a high
but there are formidable scientific and technological problems neutron flux, a high particle flux and a high thermal flux, therefore they
that have yet to be solved. Several experimental tokamaks around experience the most hostile conditions of all the materials in the fusion
the world have successfully fused hydrogen isotopes to produce reactor8,9. The plasma wall interaction issues for ITER are discussed by
energy, but all require significantly more power to heat the Roth et al.10 and Fig. 1 shows a diagram of cross-section of ITER, with
plasma than is produced by the fusion reaction. The Joint European the current material selection. The magnetic field in a tokamak confines
Torus (JET) currently holds the record of producing 16 MW for an the plasma and keeps the hot (100 million °C) ions and electrons away
input power of 24 MW. ITER (International Tokamak Experimental from the vessel walls. Some plasma ions do, however, diffuse across the
Reactor)2, due to be commissioned in Cadarache in 2018, will be field lines collide with the walls. The grey shaded region shown in Fig. 1
the first fusion experiment that will produce more power from represents the region of the vessel where the magnetic field lines are
the fusion of deuterium and tritium (DT fusion) than will be open, that is they terminate on the vessel walls. This field configuration
used the heat the plasma to the required temperature (around is designed to direct, or divert, particles that escape from the plasma
100 million °C). The goal is to produce ten times as much power to a particular part of the vessel where they can be removed in a
than is consumed; 500 MW of power with a pulse length of seven controlled way. The region of the vessel the particles are directed to
minutes. The energetic (3.5 MeV) alpha particles that are produced is known as the divertor. The divertor experiences exceptionally high
by DT fusion will heat the plasma by ionic collisions, which will thermal and particle fluxes and presents an enormous challenge for
compensate for radiation losses and result in a self-sustained materials selection.
reaction. Plasma facing materials have two main roles; they protect the first
ITER is, however, still fundamentally a plasma experiment. It will wall from the high particle flux and they transport thermal energy
not produce electricity. The next step on the road to fusion power will away from the surface. These roles lead to the requirements of
be to design and build a demonstration power plant which will present
new challenges. The tritium required to fuel the reaction has to be
produced in situ and the fusion energy must be converted to electricity.
Last, but not least, materials will be required that will be able to
withstand the extremely hostile environment without significant
degradation in their functional properties3-6.
Some of the radiation effects experienced by materials in fusion
power plants will be similar to those experienced in fission power
plants; the radiation enhanced embrittlement of metals caused by
the obstruction of dislocation motion by radiation defects in metals,
for example. Other effects are unique to fusion materials. The high
energy (14 MeV) neutrons produced by the fusion reaction penetrate
the wall to a depth of around 15 cm7 and result in transmutation
events. Transmutation produces copious quantities of gas (H, He),
which is insoluble in the material and will eventually degrade the
properties. These effects are discussed by Samaras in this issue. The
conditions experienced by the materials that line the wall of the
vacuum vessel are also unique to fusion reactors. These materials,
known as plasma facing materials, will experience extreme heat and
particle flux. The development materials that will withstand such
conditions is one of the main challenges faced by designers of future
fusion power plants.
In this review we summarise the conditions experienced by
plasma facing materials and the current choice of materials. We
describe how materials modeling can contribute to the understanding Fig. 1 Diagram of the cross-section of ITER, showing the confined plasma (red)
of the effects of the high thermal and particle flux on the materials and the plasma facing materials (Be, blue; W, purple; C, black). The area
shaded grey shows the region where the magnetic field lines terminate at the
and finish with a discussion of the areas where further research is divertor to direct particles that escape from the plasma away from the wall of
required. the vacuum vessel11.

NOVEMBER 2009 | VOLUME 12 | NUMBER 11 39

REVIEW Modeling plasma facing materials for fusion power
high thermal conductivity and high resistance to erosion by particle
bombardment12,13. Some of the atoms will be ejected, or sputtered,
from the wall and enter the plasma. These atoms will be stripped of
their electrons and cause radiative cooling of the plasma. The lower
the atomic number of the atoms the lower the cooling, therefore low
atomic number (low Z) materials are favoured from the perspective
of the plasma. However low Z materials tend to have low cohesive
energies and so they are susceptible to sputtering. The contradictory
requirement of low Z to minimise plasma cooling and high Z to
minimise erosion is typical of the challenges faced by reactor designers.
Carbon has traditionally been used as a plasma facing material
because it has a favourable combination of low Z, high thermal
conductivity and strong bonding. It has, however, a significant
disadvantage; its susceptibility to chemical sputtering by hydrogen
isotopes14. Chemical sputtering is the process whereby ion
bombardment enhances, or enables, a chemical reaction between
the bombarding species and the surface atoms, resulting in weakly
bound molecules15,16. The energy threshold for chemical sputtering is
significantly lower than that of physical sputtering, where atoms are
ejected from the surface via elastic collisions. The rate of chemical
sputtering is enhanced by bombardment with other ionic species, which
is a particular problem in a fusion reactor. Bonds that are broken by the
bombarding ions are instantly passivated by the hydrogen isotopes in
the plasma, resulting in weakly bound hydrocarbon species17,18.
The main concern is not the erosion of the plasma facing material,
but the tritium inventory19. Safety and resource considerations mean
that the majority of the tritium used to fuel the fusion reaction must
be accounted for at the end of the experiment. Any tritium that reacts
with the carbon surface, to form volatile hydrocarbons, will redeposit
elsewhere in the reactor vessel and it will be difficult to trace and
recover. Tokamaks with metal walls have displayed a huge reduction
in the tritium inventory20, in comparison to tokamaks lined with
graphite coated tiles. For this reason carbon, in the form of carbon fibre
composites, is only used for the strike points (the region where the flux
lines intersect the wall) in the ITER design (Fig. 1).
The low atomic number of beryllium makes it a prime candidate
for a plasma facing material and it is used as a lining for the first wall
in the ITER design (Fig.1). Be has the disadvantage of low resistance to
sputtering and low melting temperature and therefore it is not used
in the divertor region, where the particle flux is highest. One major
concern is that a plasma instability could cause a sudden increase in
the thermal load which would melt the beryllium and severely damage
the plasma facing material.
The high erosion rate of beryllium means that it is unlikely to be
suitable for a commercial power plant, therefore alternatives need to
be considered. Tungsten, a refractory metal with high resistance to
sputtering, high thermal conductivity and high melting point, may be a
viable alternative21. It is used in the divertor region in the ITER design
and it is being considered as first wall armour for future designs. The
40 NOVEMBER 2009 | VOLUME 12 | NUMBER 11
main disadvantage is the potential for tungsten to contaminate the
plasma and cause large radiative losses.
Diamond is also being considered as a possible plasma facing
material22. The exceptionally high thermal conductivity, low thermal
expansion, high resistance to sputtering and low Z make it a strong
potential candidate. Preliminary experiments on diamond coated tiles
look promising23,24 although their long term durability has not been
established. A particular concern is the resistance to graphitisation
and amorphisation under high heat and particle flux. Such damaged
material would be susceptible to chemical sputtering.
Modeling plasma facing materials
Thermal flux
The divertor region of a fusion reactor will experience extremely high
thermal flux. In ITER, the thermal flux will be 10 MW m-2 during normal
operation13 and even higher during plasma disruptions. This energy
must be transported away from the surface efficiently in order to avoid
surface melting. The divertor is actively cooled by water to extract the
energy from the reactor and an accurate model is required to calculate
the temperature distribution under various scenarios. Finite element
programs are used solve the heat diffusion equation using numerical
methods (Cast 3M25 for example). The HEIGHTS computer package26
calculates 3-dimensional temperature distributions of materials in
response to energy distribution processes and it includes the effects of
surface vaporization, phase changes and heat transfer to the coolant.
An example of the temperature distribution in a copper mock-up is
shown in Fig. 2. Such thermal diffusion models play a valuable role in
the validation of divertor designs but they are sensitive to the material
parameters input to the model. The thermal conductivity of most
materials is well characterised under normal equilibrium conditions at
reasonable temperatures, however divertor materials experience very
high temperatures and they are far from equilibrium. The thermal
conductivity will decrease over time as radiation damage accumulates
in the materials and the defects scatter the electrons and phonons27,28.
Heat transfer coefficients across interfaces between different materials
are less well characterised than thermal conductivities and these will
also degrade as radiation defects accumulate at the interfaces.
Another area of concern is the effect of high thermal load on the
microstructure and crystal structure of the plasma facing materials. The
recrystallization of tungsten alloys could be one of the main limitations
to the upper operating temperature of a tungsten divertor30. Diamond,
a potential plasma facing material, is metastable with respect to
graphite and the crystal structure will transform if held at a high
enough temperature for a sufficient time period. Such transformations
can be investigated using molecular dynamics simulations, by gradually
increasing the simulation temperature. This method has been used to
investigate the stability of the diamond structure for different surface
terminations and doping levels. An example of the results of such a
simulation is shown in Fig. 3.
 Modeling plasma facing materials for fusion power
Fig. 2 Temperature distribution (calculated using the HEIGHTS code) of a copper mockup with 5mm W coating (inlet water temperature of 403 K, water flow
velocity of 12ms−1) for 60 MJ m−2 deposited energy of 0.5 s duration29.
Fig. 3 A (111) diamond surface with hydrogen terminated bonds on half of
the surface, heated to 2034 K, at a rate of 6.8 K ps-1. 3 coordinated C atoms
are shown in blue, 4 coordinated C atoms are shown in orange and H atoms
are white. The clean part of the surface has transformed to graphite but the
diamond structure was maintained on the hydrogen terminated part of the
slab, demonstrating the stabilising effect of hydrogen termination (Dunn and
Duffy, unpublished results).
Sputtering
The erosion caused by the high flux of atoms and ions experienced
by plasma facing materials is a major concern for future fusion power
plants. The particle flux is predicted to be of the order of 1018 m2 s-1
at the first wall and 1024 m2 s-1 (10-6 nm-2 ps-1)13 of ITER. Most of the
particles will have energies of a few eV but the energy spectrum could
spread to a few keV31. Particles that impact the surface impart some of
their energy to the atoms near the surface of the material and, if this
energy is high enough to overcome the surface binding energy, atoms
REVIEW
will be ejected, or sputtered, from the surface. The number of atoms
ejected from the surface (the yield) can be estimated from transport
theories of Thompson32 and Sigmund33 or calculated using computer
simulations34-36. Computer simulations fall into two classes; those
based on the binary collision approximation (BCA) (MARLOWE37, TRIM
SP38), where the collisions between the atoms are approximated by
two-body elastic collisions, and those based on molecular dynamics
(MD). MD simulations are more computationally expensive than BCA
simulations but they provide a much greater level of detail about the
basic mechanisms and the surface damage. The simulation is initiated
with an atom a short distance above the surface of a crystal and the
atom is given a velocity directed towards the surface. The damage
created in the crystal and the number of sputtered atoms can be
monitored as the simulation progresses.
The type of damage created by a bombarding atom is sensitive to
the position and direction at which the atom bombards the surface
and to the bombarding energy39. For single crystals, particular impact
directions result deep penetration into the crystal between the
atomic planes and few sputtered atoms, a process which is known as
channelling40. Linear cascades occur at relatively low energies, when
only binary collision events are relevant, and they result in little surface
damage and a small number of sputtered atoms (Fig. 4a). When the
energy is high, many body collisions are important and a thermal
spike, a disordered liquid-like region, forms in the material. When the
thermal spike forms close to the surface of the material the “hot”
atoms are ejected from the surface and the sputtering yield is high
(Fig. 4b). A detailed analysis of the damage during the simulation helps
to elucidate the dominant mechanism. Linear cascades are described
well by the binary collision approximation, where each collision is
NOVEMBER 2009 | VOLUME 12 | NUMBER 11 41
REVIEW Modeling plasma facing materials for fusion power

(a)

(b)

Fig. 4 Schematic representation of surface damage caused by different types of sputtering events. (a) represents a linear cascade where 2- body collisions
dominate. (b) shows the thermal spike where high deposited energy creates a disordered region of the crystal, which results in sputtered atoms and adatoms.

considered to be an independent event, but more complex models are

required for the regime where many body effects are important41. (a)
Classical molecular dynamics simulations represent the interactions
between atoms by interatomic potentials, which range from simple
two-body potentials, that depend only on the interatomic separation
of two atoms, to more complex embedded atom or environment
dependent potentials, in which the interaction between two atoms
depends on the position of their neighbours. Any role the electrons
have in the material is included only at the level of the interatomic
potentials. In some situations the electrons have a more active role
that cannot be described by classical potentials. This was noted for
(b)
sputtering42 and cascades43-45 several decades ago and there has
recently been a revival of interest in these effects as computational
power has increased and sophisticated theoretical techniques have
been developed46. The electrons have a number of related roles.
They act as a viscous medium that removes energy from moving
atoms44,45,47, they store and transport this energy and redistribute it
to the atoms. Different approaches have been developed to include
these effects in cascade48 and sputtering simulations49 but a complete
description is still lacking. Recent simulations have demonstrated that
the damage resulting from ion bombardment of metals is very sensitive
to the thermal transport properties of the electrons (Fig. 5)50 and
the stopping power of the metal51. Fig. 6 shows the evolution of the
electronic energy during the early stage of a sputtering simulation of
Ag52. For a typical cascade simulation the electronic temperature is out Fig. 5 Vacancies (gold) and interstitials (blue) created by bombarding a
of equilibrium with the lattice for several picoseconds53. W (111) surface with a 5 keV W atom. In simulation (a) the total energy
is conserved whereas in (b) energy is exchanged with the electrons. The
Sputtering simulations are generally carried out in a vacuum at simulations demonstrate how energy transport and storage by the electrons
room temperature, very far from the conditions in a real reactor. affect surface damage. (Data taken from50).

42 NOVEMBER 2009 | VOLUME 12 | NUMBER 11

 Modeling plasma facing materials for fusion power
Fig. 6 Snapshots of a 5 keV Ag → Ag(111) bombardment. The atoms are
represented by blue (bulk) and green (surface) dots and the electronic energy
density (eV Å–3) is represented by a colour map52.
Some simulations have been performed at high temperatures54,55 but
the effect of high temperature and presence of the plasma on the
sputtering yield and surface damage has not been fully investigated.
The plasma may enhance the sputtering yield because the ejected
atoms will be ionised by the plasma and the charged ions will
accelerate towards the surface under the influence of the local electric
field, knocking further atoms from the surface56. The effects of the
synergy between the plasma, heat flux and particle flux on surface
erosion requires further investigation.
Chemical sputtering
The previous section discussed how molecular dynamics is used to
model physical sputtering, when atoms are ejected from surfaces by
elastic collisions with bombarding particles. In the case of chemical
sputtering the bombarding particles undergo a chemical reaction
with the surface atoms, which weakens the binding to the surface.
Such reactions are challenging to simulate using classical molecular
dynamics, but significant progress has been made in recent years on
the development of interatomic potentials that can describe bond
breaking and forming accurately. The REBO57, EDIP58 and AIREBO59
REVIEW
(a)
(b)
Fig. 7 Schematic representations of two chemical sputtering processes on
graphitic carbon. In (a) two H (blue) atoms bond to a C atom (grey), a 3rd
H atom has sufficient kinetic energy to break the C bond and create a weakly
bound methyl group, which subsequently desorbs from the surface and reacts
with H to form methane. In (b) four H atoms bond to neighbouring C atom.
A fifth H atom breaks the neighbouring C-C bond and the ethene molecule
readily desorbs from the surface.
potentials for hydrocarbons are all suitable for modeling chemical
sputtering of carbon.
The surface erosion of a-C and graphite has been studied using
molecular dynamics60,61. Many types of reaction of low energy H are
possible, depending on the bonding conformation of the surface atoms.
Two particular examples are shown in Fig. 7. Low coordinated surface
atoms will be particularly susceptible to chemical sputtering due to
weaker binding and their affinity for H.
One of the major advantages of modeling is that it can be used
to investigate processes at a level that is inaccessible to experiment.
Detailed analysis of sputtering simulations have resulted in the
discovery of swift chemical sputtering, where a hydrogen atom moves
between two bonded carbon atoms and consequently breaks the
bond62. The process only occurs for a well defined range of energy. If
the energy is too low the atom cannot penetrate the bond and if it
is too high it spends too little time between the atoms to break the
bond. The bond breaking does not necessarily eject the atom but, when
combined with other interactions, the mechanism makes a significant
contribution to the sputtering yield.
Modeling studies suggest that the susceptibility of diamond to
physical sputtering is comparable to the (0001) surface of graphite63
but models of chemical sputtering have not yet been published for
diamond. Experiments have demonstrated that diamond is more
resilient to low energy hydrogen bombardment than other forms of
carbon64, although this may be due to surface impurities. Radiation
damage may, however, decrease its resilience due to modified surface
structures and defects, and the high thermal flux may result in
structural transformations (section 2). The divertor region experiences
high particle flux, particularly alpha particles, which will damage
the surface and decrease the resilience to chemical sputtering, as
NOVEMBER 2009 | VOLUME 12 | NUMBER 11 43
REVIEW Modeling plasma facing materials for fusion power
was found for Ar bombardment of graphite17,18. Enhanced physical
sputtering in the presence of low energy hydrogen has been observed
in MD simulations65.
Outlook
The erosion of plasma facing materials could be one of the main
factors that influences the operational schedule of experimental
fusion reactors and future power plants66. The materials selected
for current designs will not withstand the conditions of a power
plant for a commercially viable period of time, therefore further
materials development is essential. The design and development
of plasma facing materials will require a detailed understanding
of the processes that occur when a material surface is bombarded
with an intense flux of heat, particles and neutrons simultaneously.
Modeling will play a major role in this development, by using
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31. Kotov, V., et al., J. Nucl. Mater. (2009) 390-391, 528.
32. Thompson, M. W., Phys. Rep. (1968) 18, 377.
33. Sigmund, P., Phys. Rev. (1969) 184, 383.
34. Urbassek, H. M., Nucl. Instru. Meth. B (1997) 122, 427.
44 NOVEMBER 2009 | VOLUME 12 | NUMBER 11
methods ranging from ab initio techniques, to understand fundamental
mechanisms, to macroscopic materials modeling, to evaluate the
stress and temperature distribution of real components. The synergy
between the various radiation effects (the decrease in thermal
conductivity due to radiation damage, the increase in sputtering in
the presence of a plasma and the increase in chemical sputtering by
ion bombardment, for example) presents enormous challenges for
both experiment and theory. Nevertheless, an integrated approach
involving modeling, testing and design67 should enable the problems
to be overcome and the dream of commercial fusion power to be
realised.
Acknowledgements
We acknowledge support from EPSRC and the European Communities
under the contract of Association between EURATOM and CCFE.
35. Eckstein, W., and Urbassek, H. M., Topics in Applied physics, (2007) 110, 21.
36. Urbassek, H. M., Topics in applied physics, (2007) 110, 189.
37. Robinson, M. T., and Torrens, I. M., Phys. Rev. B (1974) 9, 5008.
38. Biersack, J. P., and Eckstein, W., Appl. Phys. A (1984) 34, 73.
39. Ghaly, M., et al., Phil. Mag. A (1999) 79, 785.
40. Robinson, M. T. and Oen, O.,S., Appl. Phys. Lett (1963) 2, 30.
41. Harrison, D. E., Crit. Rev. Sol. State and Mater.Sci. (1988) S1.
42. Jakas, M. M., and Harrison, D. E., Phys. Rev. B (1985) 32, 2752.
43. Flynn, C. P. and Averback, R. S., Phys. Rev. B (1988) 38, 7118.
44. Caro, A., and Victoria, M., Phys. Rev. A (1989) 40, 2287.
45. Finnis, M. W., et al., Phys. Rev. B (1991) 44, 567.
46. le Page, J., et al., J. Phys: Cond. Matt. (2008) 20, 125212.
47. le Page, J., et al., (2009) New J Phys. 11, 013004.
48. Duffy, D. M., and Rutherford, A. M., J. Phys: Cond. Matt. (2007) 19, 016207.
49. Duvenbeck, A., and Wucher, A., Phys. Rev. B (2005) 72, 165408.
50. Khakshouri, S., and Duffy, D. M., Phys. Rev. B (2009) 80, 035415.
51. Sandoval, S., and Urbassek, H. M., Phys. Rev. B (2009) 79, 144115.
52. Duvenbeck, A., et al., New J. Phys. (2007) 9, 38.
53. Rutherford, A. M., and Duffy, D. M., J. Phys: Cond. Matt. (2007) 19, 496201.
54. Rosencrance, S. W., et al., Phys. Rev. B (1996) 53, 2378.
55. Liang, J. H., et al., Nucl. Instru. Meth. B (2003) 202, 195.
56. Umstadter, K. R., et al., J. Nucl. Mater. (2007) 386-388, 751.
57. Brenner, D. W., et al., J.Phys. Condens. Matt, (2002) 14, 783.
58. Marks, N. A., Phys. Rev. B (2000) 63, 035401.
59. Stuart, S. J., Tutein A. B. and Harrison, J.A. J. Chem. Phys. (2000) 112, 14.
60. Salonen, E. Physica Scripta (2004) T111, 133.
61. Nordlund, K., Phys. Script (2006) T124, 53.
62. Salonen, E., et al., Phys. Rev. B (2001) 63,195415.
63. Smith, R., Proc. Roy. Soc. (1990) 431, 143.
64. Donnelly, C. M., et al., Diamond & Related Materials (1997) 6, 787.
65. Maya, P. N., et al., New J. Phys. (2008) 10, 023002.
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 Multiscale Modelling:
the role of helium in iron
The mechanisms and processes of bubble nucleation and growth are
still not completely solved and research in this field is ongoing. This is an
important issue for materials used in fission and fusion reactors. In such
environments, one of the main gaseous by-products is helium, whose
presence and further production is known to decrease ductility, fatigue life
and weldability, induce creep and stress rupture properties of materials,
as well as promote swelling. These effects lead to the drastic modification
of the material’s mechanical properties. In the past, experiments have
been used to offer clues into the structure of the materials; now,
modelling offers the possibility to understand the structure of the material
and from this information, to elucidate a fundamental understanding of
material properties. 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
HT-MAT, LNM, NES, Paul Scherrer Institute, Switzerland
Email: maria.samaras@psi.ch

Confronted with an exponentially growing populous of energy
consumption, and the need to reduce CO2, peaceful nuclear
energy facilities (both fission and fusion) have been labelled as a
piece of the future energy pie solution1. Materials development
and design have been pinpointed as one of the limiting factors
in extending the lifetime of current reactors and optimising
future reactors2,3. As material and financial resources become
limited, the large experimental programs undertaken in the past
have become too expensive to operate. Furthermore, traditional
modelling concepts of materials prediction based on constitutive
equations, are reaching their limitations. Thus a new ideology
has evolved to understand the basic physics and chemistry of the
material and incorporate the processes and mechanisms occurring
at smaller time and length scales, to try and understand the
properties of the material. Relevant processes encompass a range
of scales from the pico- scale to length scales of large components
and time scales of 60-100 years. Modelling such a broad range of
issues on relevant length and time scales requires a multiscale
modelling approach coupled with validation experiments4-7
e.g. see Fig. 1.

46 NOVEMBER 2009 | VOLUME 12 | NUMBER 11 ISSN:1369 7021 © Elsevier Ltd 2009

 Multiscale Modelling: the role of helium in iron REVIEW

Fig. 1 Looking at the figure clockwise: 1) from a nuclear power plant2, a small sample can be cut 2) into a micropillar of tens of mm108. Modelling reduces the size
investigated further and looks at 3) Molecular Dynamics simulated samples (3) of tens of nm (4) with grain sizes of 12nm. This enables studies of atomistic events
of, for example, irradiation with the production of defects (5). To understand the stability and mobility of such defects it is important to study the interatomic forces
present using small samples of up to 100 atoms using (6) DFT calculations of the elements of interest.

Materials exposed to extreme conditions undergo deformation
processes of the microstructure which lead to hardening, swelling,
fracture, creep, blistering, corrosion and a loss of ductility, with a
shift in the ductile to brittle transition temperature (DBTT)8. For a
more detailed discussion of these issues, the readers are referred to
the other papers in this edition9-11. In an irradiation environment, a
material is constantly bombarded by high energy neutrons which leads
to radiation damage and to the production of helium. Helium affects
structural materials, cladding and fuels. The presence of helium in
metals can drastically alter their mechanical properties, even at low
concentrations12. Helium acts as a precipitate due to its extremely
low solubility13 and as a consequence interacts with microstructural
features such as voids present in the material14. Void formation is a
microstructural phenomenon that is sensitive to the helium production
rate15 and bubble nucleation comes as a natural consequence which
leads to the material’s degradation. Once inside a vacancy, helium
is known to be deeply trapped therein, decreasing its mobility and
enhancing the aggregation of further vacancies and helium atoms
which can be trapped at dislocations and grain boundaries (GBs)16,17.
The effect of helium is of concern over a wide range of
temperatures. At high temperatures the clustering of helium bubbles
in GBs results in embrittlement. The creep lifetime expectancy of a
material is also affected by the accumulation and fast diffusion of
helium in GBs. Indeed, segregation of precipitates into bubbles can
induce both trans- and inter-granular brittleness even in intrinsically
ductile materials. Swelling driven creep is closely related to void
swelling. Experiments and continuum models on bubble formation and
helium embrittlement have been found to be limited in the information
that can be obtained from them.
These issues clearly indicate the necessity to understand the
dynamical processes involved in bubble nucleation and growth. As the
events occur on a variety of time and length scales, modelling provides
the perfect setting in which to investigate such issues. To present the
modelling toolbox as a multiscale approach, this review will focus on
the modelling efforts performed to investigate He bubbles. Due to
the plethora of candidate materials and simulations performed, the
review will centre on He effects in ferritic steels. Although ferritic (bcc)
materials are resistant to swelling18, the role of helium, helium-vacancy
(He-V) clusters and helium bubbles in the ferritic steels, irradiation
hardening, swelling, crack nucleation and cleavage fracture are only
partially understood. Such phenomena are important factors that need
to be evaluate when determining the lifetime of a material in a reactor.
A multiscale modelling methodology is applied by implementing
density functional theory (DFT) and molecular dynamics (MD) to
obtain the energetics and state of He, Feint-He and He–V clusters
in Fe; kinetic Monte-Carlo (KMC) techniques to understand the
thermal stability and migration behaviour of the clusters with a direct
comparison to thermal He desorption spectrometry (THDS); rate
theory (RT) methodologies to investigate longer term diffusion and
growth mechanisms; dislocation dynamics (DD) to study issues of
hardening through studies of He bubble–dislocation interactions; and
continuum methodologies to investigate issues such as embrittlement,
in order to obtain lifetime predictions (as shown schematically in Fig.
2). The investigations undertaken with these methods will now be
discussed in more detail. The references cited herein are examples
rather than a comprehensive bibliography of the work undertaken in
studies of helium in iron.
Microstructure
Energetics
In bcc metals, studies of the mobility of helium carried out with
atomistic simulations date back to Rimmer and Cottrell19. Two main

NOVEMBER 2009 | VOLUME 12 | NUMBER 11 47

REVIEW Multiscale Modelling: the role of helium in iron

configurations have been seen to contribute to helium accumulation - Table 1 Presents the formation energies of a
interstitial helium with low migration energy, and substitutional helium substitutional and interstitial (octahedral and tetrahedral
which has a large trapping energy. More recently, DFT calculations have position) helium atom in an iron matrix. The top two
been employed to study the dissolution and migration mechanisms and results are DFT calculations, and the rest of the results
energies of helium in iron20. Such studies reveal that the tetrahedral are calculated from empirical potentials. The second and
site is energetically more favorable for the He interstitial than the
third columns describes the Fe-He and Fe-Fe potentials
used. FS stands for Finnis Sinclair; D-D for Dudarev-
octahedral site20,21.
Derlet. All calculations use the Beck He-He potential.
Magnetism stabilised the bcc iron matrix and affects the stability
of self interstitial clusters formed. As such the role of magnetism on Fe-He Fe-Fe Oct Tetr Subs
helium in iron has been investigated by DFT calculations, where some DFT Seletskaia 4.60 4.37 4.08
authors believe it influences the movement of helium atoms in the iron Fu 4.57 4.39 4.22
matrix21. This has been refuted20 and very recently shown to have a MD J-N AMS 4.512 4.385 4.099
negligible influence23. Thus at zero Kelvin, an Fe-He potential doesn’t
J-N D-D 4.444 4.326 4.212
explicitly need to include magnetism. As the temperature increases,
J-N FS 4.406 4.290 4.116
however, the role of magnetism in Fe-He interactions cannot be
Wilson FS 5.25 5.34 3.25
calculated within the DFT framework. Indeed, in the next paragraph
Seletskaia FS 4.54 4.5 3.91
the reasons for including magnetism in fitting an Fe-He potential will
become apparent. Yang FS 5.25 3.25

Although, DFT calculations provide more accurate values of the
solution, migration and nucleation properties of helium in a bcc iron
matrix24 compared to MD simulations25, MD is necessary to investigate
larger system sizes and times. In MD, the forces between atoms are
provided by empirical potentials. Unfortunately, earlier Fe-He empirical
potentials22,26 produce the octahedral site as the most stable interstitial
helium position, in contrast to DFT calculations. More contemporary
Fe-He empirical potentials27,28 are fitted such that the most stable
helium interstitial sits at the tetrahedral position. Table 1 shows results
Morishita FS 5.25 5.34 3.25
for interstitial and substitutional helium energetics obtained by DFT
and MD simulations (with the Wilson, Seletskaia, Juslin Nordlund (J-N)
Fe-He potentials, Beck He-He potential29 and Ackland (Finnis-Sinclair
type)30 and Dudarev-Derlet (D-D)31 Fe-Fe potentials ).
As table 1 shows, to study helium in iron with MD, it is also
necessary to include Fe-Fe30-32 and He-He29,33 potentials. For Fe-Fe
interactions, magnetism influences the stability of the interstitial

Fig. 2 Studying helium in the iron matrix on the multiscale- figure taken from5 and references therein. Various computing facilities are used for the modelling
(e.g.109). DFT calculations are used to calculate binding energies as a function of helium20. MD simulations can study larger helium clusters and helium going to
GBs41. At atomistic longer time and length scales, rate theory allows results such as the fraction of release of helium104. Moving to the mesoscale, DDD calculations
provide information on the critical shear stress of a dislocation moving through a field of ODS and He particles and reveals the role of helium in the sample89. The
ultimate goal being to reproduce what is seen experimentally: e.g. TEM samples110.

48 NOVEMBER 2009 | VOLUME 12 | NUMBER 11

 Multiscale Modelling: the role of helium in iron
defects formed24,34,35. To investigate issues such as loop punching,
where iron self interstitials are created (see below), a proper description
of iron interstitials needs to be included in the MD simulations
(provided by the Mendelev32 or the magnetic D-D31 Fe-Fe potentials).
State of He-V clusters
MD simulations using (Ackland-Wilson-Beck (A-W-B)) potentials
found that interstitial helium jumps into vacant lattice sites, becoming
substitutional with a large binding energy (strongly trapped) and
forming a He-V cluster36,37, in agreement with DFT calculations37.
Helium is strongly bound to the He-V cluster and can stabilise it,
thus increasing its lifetime by reducing thermal vacancy emission36,38.
Interestingly, the position of He in a di-vacancy is delocalised with a
symmetrical location preferred over a vacant lattice site39.
DFT has shown that small He-V clusters (up to 4 helium) will lead
to bubble nucleation in initial vacancy-free lattices20. MD simulations
have enabled the investigation of larger numbers of helium atoms and
found that 6 helium atoms in the matrix induces the kick-out of an
iron atom26. This phenomenon occurs when helium interstitial atoms
are placed at a far distance in the case of the Wilson26 and Seletskaia
(less frequently)21 potentials but only when the He interstitials are in
close proximity for J-N27,40,41. Comparison of the Fe-He Wilson and
Seletskaia potential showed a difference in the point defect and Fe-He
cluster creation42. As the Seletskaia Fe-He potential overestimates
the formation energies of Fe interstitials24, the kick-out of the iron
interstitial requires larger energy and will occur less frequently than
with the Wilson potential. As the Seletskaia potential is least accurate
at describing the properties of iron in the interstitial region, it is not
the ideal potential for investigating this phenomenon. As the vacancy
formation energy in iron is 2.15 eV43, under ambient conditions a He-V
cluster may absorb vacancies from the surrounds rather than produce a
self-interstitial atom or a SIA loop through the kick-out mechanism.
Helium bubbles
Helium bubble investigations find that the binding energy of helium
to the cluster is independent of the cluster size but dependent on the
(helium to vacancy) He/V ratio (A-W-B potential)36. The binding energy
is found to increase with more helium, such that the helium increases
cluster lifetime by reducing thermal vacancy emission. When the He/V
ratio is high (He/V >10)38, the pressure in the bubble is so large that
there is spontaneous creation of vacancies due to their low formation
energy43 and therefore the thermal emission of self interstitial atoms
(SIA) and SIA clusters (emission energy of SIA is 4.88eV36) and helium
(emission energy 5.25eV36). These SIAs preferentially form in prismatic
loops as shown by the simulation of a 20-He clusters which induced
the kick-out of a 5-17 SIA loop38. A study of dissociation energies
surrounding He-V clusters was undertaken with a comparison of
potentials (A-W-B; A-JN-B, DD-W-B; DD-JN-B)44, finding that only the
(A-JN-B) potential agrees with DFT calculations.
REVIEW
When comparing small helium bubbles, DFT obtained a 1.3 He/V
ratio and a dissociation energy of 2.6eV45. MD simulations predict a
ratio of 1.8 and a dissociation energy of 3.6 eV (A-W-B potential)36. As
the bubble size increases, the equilibrium helium pressure in the bubble
decreases46,47. Larger He clusters have lower He/V ratios44,48-50, and
emit SIAs (and SIA clusters) more easily, leading to loop punching43.
Such results clearly show that nucleation and growth phenomena need
to be separated.
For large helium bubbles with low He/V ratio, where the bubble
is stable, surfaces take on a polyhedral morphology51; such faceting
has also been seen from electron holography experiments50. The
structure of the helium in these larger bubbles was found to be in an
amorphous phase (A-W-B potential)51. Multiscale atomistic simulations
are therefore bringing forth a picture of the structure and formation of
He-V clusters and thus of helium bubbles.
Radiation damage of single crystal
When compounded with the presence of irradiation and defects
produced therein, the system becomes more complex. In an irradiation
environment, a material is constantly bombarded by high energy
neutrons, which leads to radiation damage and to the production of
helium. At low temperature, irradiation can lead to radiation hardening
and embrittlement. At high temperatures, irradiation has less of an
effect on the material, however, since all materials are exposed to a
large range of temperatures as a consequence of reactor shut downs
and start ups, these materials will also be subjected to radiations at
low temperatures. Furthermore, for modelling purposes, irradiation
simulations introduce defects in a non-preempted manner, and are
therefore a good method of investigating short timescale helium -
defect interactions.
Radiation is introduced in atomistic samples by simulating
displacement cascades with MD. Such simulations provide a 3D
visual landscape of the density and proximity of defects in relation
to the primary knock-on atom (PKA) which takes full impact of the
collision in terms of an energy and a direction. Such simulations have
been performed with pre-existing substitutional He (1-5% He)53-57;
0.1%He58,59 as a function of temperature (100 K53,54 – 600 K55,
10-523 K59); with interstitial He58,59; and with HenVm clusters56,57.
Simulations look at a range of 500 eV – 40k eV PKAs (A-W-B
potentials). It was found that helium doesn’t influence the
Frenkel pair production and that that there is no difference in
interstitial or substitutional He during the collisional state, but
differences occur in the distribution of iron dumbbells during the post
collisional stage60.
As a substitutional helium atom moves to neighbouring vacancies
with 0.015 eV36, during a melt where many Frenkel pairs are produced,
helium will move very quickly. Additionally, helium atoms knocked
or activated from their substitutional position into an interstitial
position during the irradiation will also move quickly (interstitial helium
NOVEMBER 2009 | VOLUME 12 | NUMBER 11 49
REVIEW Multiscale Modelling: the role of helium in iron
activation energy is 0.078eV36). If these helium atoms move to the
periphery of the cascade they will not be able to recombine with the
vacancies situated in the cascade core. With the removal of 5% Fe
atoms to include 5% substitutional He atoms, such fast mobility away
from the cascade core is indicative that a larger number of vacancies
and vacancy clusters will be formed than in the displacement cascades
performed at the same PKA energy in defect free, single crystal
matrices. This is similar to irradiation damage simulations performed
in nanocrystal iron, where the presence of GBs with free volume
therein led to the formation of larger vacancy clusters than seen in the
single crystal simulations61. Additionally, one study showed that the
helium will also be trapped by iron interstitials, such that the helium
cannot move into substitutional positions and will thus produce more
vacancies in the matrix60. Interestingly, what is not discussed in any of
these papers is the final configuration of the helium and how it clusters
within the vacancies as well as the He/V ratio. Furthermore, it would
also be interesting to know the spatial range from the PKA atom which
encompasses the affected He and how far outside of the displacement
core this reaches.
Studies went on to investigate the effects of irradiation damage
on pre-existing He-V clusters and found that the resulting damage
is He/V ratio dependent (based on A-W-B potential simulations).
A high He/V ratio leads to a larger vacancy cluster since Frenkel
pair recombination is not possible57) and due to the decrease of
iron binding energy to a He-V cluster36. A small He/V ratio led to
dissolution of the cluster as a result of the kick out of helium (during
the collisional phase)56, such that vacancies recombine with nearby
iron atoms. This is in agreement with DFT calculations which show that
clusters with large He/V ratios tend to emit He interstitials and clusters
with low He/V ratios tend to emit vacancies45. The He/V ratio differed
in the core of the cascades, where it was less than one, and at the
periphery of the cascade they were greater than one62.
It is important, to note that the discussions on the stability of He-V
clusters which are irradiated53,55 can only focus on the helium and iron
movement within the simulation samples since the vacancies do not
move throughout the simulation timeframe (20ps). The independence
of the mean size of the He-V clusters remaining after irradiation55,
which contradicts experimental results63,64, could be a consequence
of the timeframe used, since the vacancies have not had the time to
collapse into their more stable configuration, the potential used and/or
the visualization method implemented to define vacancies (which also
plays a role in the interpretation of the results).
On the longer spatial and time scales, bubble super lattices form
as a consequence of irradiation65. These spatially self-organised
microstructures have been described using stability theory and non-
linear dynamics in terms of the Ginzburg-Landau type equation66,67.
Results found that the cavity structure adopts the same 3D structure as
the host lattice67. Combining these results, a picture of bubble growth
and dissolution in the presence of irradiation slowly evolves.
50 NOVEMBER 2009 | VOLUME 12 | NUMBER 11
Diffusion and helium absorption at GBs
The recognition in the 1920s that atomic mobility is enhanced in
metallic GBs started a long history of GB diffusion investigations
leading to the finding that it is 4-6 orders of magnitude faster than
bulk self-diffusion. Helium bubble formation seems to occur at GBs
after annealing above 723 K68. Continuum models employed to study
GB diffusion69 cannot capture the non-uniform point defect formation
energy present in GBs. This has lead to investigating migration and
diffusion atomistically.
The study of diffusion using atomic simulations have shown that
the prevailing theory that GB diffusion is purely vacancy dominated
(similar to bulk diffusion)70, deduced from continuum calculations,
does not hold in all cases, with self-interstitial atoms also found to
influence, if not act as the dominant mechanism for diffusion70 in
certain GB structures71. An advantage of atomistic simulations is
that the atomic mechanisms of GB diffusion are not postulated but
inferred from MD simulations. GB diffusion studies show that there
are much stronger correlation effects compared to diffusion in the
regular lattice since GBs represent fast diffusion paths for helium
atoms since their defect formation energy and migration energy are
lower than in the single crystal lattice. Simulations of GBs show that
their structural properties influence their deformation and point defect
motion therein72. It is important to note that the GB is not a true sink
but is composed of regions which favour the segregation of vacancies.
Atomistic computational studies of GB diffusion therefore emerge as a
method that can overcome the limitation of experimental results and
continuum models to provide an insight of GB diffusion at an atomic
level70.
Trapping of helium by vacancies in GBs has been shown to be
rather strong in experiments73 and by simulation in nickel74 where
their accumulation in clusters of as little as five helium atoms produces
vacancy formation75 and bubble nucleation within the GB, which leads
to intergranular embrittlement76. In bcc iron, atomistic molecular static
simulations of GBs undertaken in near and symmetric GBs77 map the
helium trapping efficiency at substitutional and interstitial sites, with
interstitial helium found to be more strongly bound to the GB core
than substitutional helium. The binding energy of helium was found
to increase linearly with the excess volume in the GB, with a capture
radius to the GB of between 0.3 to 0.7 nm depending on the properties
of the GB77. Furthermore, the helium activation energies and diffusion
mechanisms are GB dependent78. The Σ3 {112} GB was found to have
the lowest GB energy and produced the lowest capture radius77.
Moving to slightly larger helium clusters, the di-He vacancy has
revealed that mobility depends on the trapping sites and the free
volume, with di-He interstitial clusters migrating rapidly along the
Σ3 GB at low temperatures, but not along the Σ 11 GB77,79. Indeed,
in the GB the di-He interstitial cluster can kick-out a SIA at high
temperatures, forming a He2V complex77,79. This is a much smaller
number of helium atoms than is needed in the single crystal, where
 Multiscale Modelling: the role of helium in iron
six helium atoms are necessary to invoke such a kick-out mechanism.
What emerges is the necessity to know the formation energy of a
vacancy in the GB of pure Fe to understand the interplay between
vacancy formation and SIA kick-out (see section 2.2).
Investigations of helium in absorption at GBs have also been
performed by RT with the inclusion of a sink strength theory80
and established that helium immobilises vacancies, formulating a
‘constrained’ model of cavity growth81. In the absence of irradiation, it
was found that GB sliding is the driving force for GB cavity nucleation.
High temperature helium embrittlement was defined as a four step
process and a mechanism for retarding GB cavity growth by limiting
GB vacancy sources by dislocation interactions was given82. However,
rate theory was not able to include higher swelling rates near GBs than
in the grain interior.
Dislocation interacting with voids and He
bubbles
Dislocation-helium interactions, the attraction of helium to dislocations
and the pinning effect of helium on dislocations are important
materials issues due to their hardening effect that contribute to the
changes of the material properties as a result of the helium present.
MD simulations of the binding energy of interstitial helium to a
screw dislocation has been calculated to be half that of the edge
dislocation83. In contrast, the mobility along both types of dislocations
is approximately the same83. Helium interstitials have been found to be
strongly attracted to the tensile region in the dislocation and jogs act
as stronger sinks84. The He/V ratio determines the binding energy of
the cluster to the dislocation as well as their trapping site85.
Simulations of large voids and helium bubbles (for MD standards)
which are visible by TEM (2 nm and above) interacting with
dislocations have been performed50,86. These simulations found that
a 2 nm void is a stronger obstacle than a He bubble with a low He/V
ratio, whereas at high He/V ratios, the He bubble becomes a stronger
obstacle [86]. Loop punching attained at the highest He/V ratio
increases the resistance of dislocation movement through the bubble
[86].
Due to the unnaturally high stresses necessary to model a
dislocation moving though a sample using MD, DDD offers a more
realistic method of studying moving dislocations. Furthermore, the
larger time and length scale of DD allow investigations of the climb
of a dislocation in a spiral path around bubbles, as can be seen in
Fig. 3 via simulation87 and experiment88. DD simulations performed
on ODS-dislocation-helium interactions show that the inclusion of
helium doubles the critical resolve shear stress89, in agreement with
experimental results90.
Microstructural evolution
He-V cluster formation and stability are studied at short time and
length scales. These He-V clusters are controlled by damage rates,
REVIEW
Fig. 3 Experimental TEM of a dislocation pinned by helium atoms. As the
dislocation breaks away from the helium bubbles, it forms spiral shapes88.
DD simulations which include climb reveal the same pattern of the dislocation
climbing around the helium atom to surpass it87.
helium production rates, fluence, sink density, temperature, and defect
parameters. To understand longer term microstructural evolution,
growth of bubbles and swelling, it is important to study phenomena
such as migration, diffusion, defect stability and interactions on longer
time and length scales which can be undertaken with KMC and RT.
Initial KMC simulations of helium in iron with vacancies found
that the helium density determined the size and lifetime of clusters,
which affect the migration of the He-V cluster36. Furthermore, it
was shown that the long term evolution of He-V clusters depends
on the initial damage state91, showing the importance of the spatial
distribution obtained from MD simulations. Such KMC results have
obtained qualitative agreement with experiment on the dependence of
temperature on swelling.
KMC simulations also show the formation of 3D He-V cluster
complexes, the 3D mobility of small He-V clusters and the role of
cluster coalescence events in assisting He-V cluster nucleation92.
Bubbles are seen to act as biased sinks for point defects, absorbing
helium and vacancies and enlarging93,94. For a review see95. Pore
formation has also recently been investigated with KMC96. Results of
KMC simulations are often made to helium desorption experiments,
which provide indirect information on the effective migration and
dissociation energy of helium and He-V clusters97.
Bubble nucleation and growth have been investigated for a long
time using RT methods, simply by studying the stability of He-V
clusters. Although, in standard RT only vacancies and single SIAs are
mobile, inhomogeneous microstructures are not described, and the
void size distribution is truncated98, the definition of bubble nucleation,
determined as occurring when 2-3 heliums bond with a vacancy99, is
NOVEMBER 2009 | VOLUME 12 | NUMBER 11 51
REVIEW Multiscale Modelling: the role of helium in iron
still valid today. Also, the importance of separating bubble nucleation
from growth using RT66 was concluded much earlier than from
atomistic simulations (see Helium bubbles section).
The production bias model (PBM)100 changed the concept of
standard rate theory by included the thermally-activated presence
of SIA clusters and vacancy clusters, which are produced directly in
displacement cascades101. PBM successfully explained high swelling
rates at low dislocation density and near GBs, finding higher swelling
rates in materials with smaller grain size. The PBM has been extended
by introducing an additional parameter which allows the inclusion of
spatial correlations between voids and other lattice defects102.
Regardless of the simplifications in RT, it is important to note that
a comparison of KMC and RT results reveal variation in results at low
temperatures, but agreement at high temperatures103. Indeed, KMC104
and RT simulations105 reveal that the characterising mechanisms are
the vacancy formation and migration energies, and that carbon is a
strong defect trapping sink95.
It is important to remember that RT has evolved to address the long
term evolution of microstructures such as helium bubble nucleation
and growth. Due to a lack of atomistic information, the models have
been limited and this has led to a shift to model the processes at
shorter time and length scales, and a move away from RT over the
past 20 years. Incorporation and linking of atomistic results discussed
in the earlier sections of this review into these well established and
evolving RT models is expected to bring forth more accurate results,
and as such a new surge of interest in the simulations possible with RT
is developing.
Embrittlement with continuum codes
Regardless of the fact that helium is not specifically included in
continuum models, in this section, continuum models will be briefly
touched upon, as it is the improvement of such lifetime assessment
codes which has triggered the large international movement of
applying atomistic and mesoscale multiscale modelling methods to
nuclear application. Lifetime assessment codes are based on a set of
variables: laboratory experimental data, constitutive laws and simple
rules. For safety reasons, these codes include generous safety margins.
Embrittlement has been investigated at large length and times
scales using DBBT (∆T) continuum models106 which includes a large
experimental database (IVAR107) and has delivered a good statistical
fit to other databases (e.g. PREDB)106. It must be noted that the
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NOVEMBER 2009 | VOLUME 12 | NUMBER 11 53
 Neutron scattering and
hydrogen storage
Hydrogen has been identified as a fuel of choice for providing clean
energy for transport and other applications across the world and
the development of materials to store hydrogen efficiently and safely
is crucial to this endeavour. 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.
Simultaneous characterisation of the structure and dynamics of these
materials during hydrogen uptake is straightforward using neutron
scattering techniques. These studies will help us to understand the
fundamental properties of hydrogen storage in realistic conditions and
hence design new hydrogen storage materials.
A. J. Ramirez-Cuesta1*, M. O. Jones1,2 and W. I. F. David1,2
1ISIS Pulsed Neutron and Muon Source, Science and Technology Facilities Council, Rutherford Appleton Laboratory, Harwell Science and
1Innovation Campus, Didcot OX11 0QX, U.K.
2University of Oxford, Inorganic Chemistry Laboratory, South Parks Road, Oxford, OX1 3QR

*Email: timmy.ramirez-cuesta@stfc.ac.uk

The reduction of our dependence on fossil fuels and global climate
change implications are amongst the toughest challenges that we
face at the beginning of the 21st century1. While we know how to
produce energy from a variety of sources, we do not have efficient
ways of storing such energy. The most efficient way of storing
energy is in its chemical form, in batteries or as hydrogen gas.
The retrieval of the stored energy is straightforward in the case
of the batteries but in the case of hydrogen requires an additional
step that may be performed via fuel cell (conversion to electrical
energy) or by burning (conversion to thermal energy). Hydrogen
can store the most energy per unit weight of any element in the
periodic table, and its potential applications as an energy vector
are essentially unlimited. It can be used to store energy produced
from sustainable energy sources during periods of low demand,
that energy then used during periods of peak demand. However,
as a gas, its volumetric energy density is very low. Consequently,
it is a great imperative to identify methods of storing hydrogen
in high gravimetric and volumetric densities. For vehicle-based
applications, a series of targets for hydrogen storage materials
have been set, and recently updated, by the Department of Energy
(DoE) of the United States to be used in the freedom car2, and
these are summarised in Table 1.
Hydrogen can be stored as a gas in high pressure vessels and
also as a liquid. However, because of its low density at room

54 NOVEMBER 2009 | VOLUME 12 | NUMBER 11 ISSN:1369 7021 © Elsevier Ltd 2009

 Neutron scattering and hydrogen storage REVIEW

Table 1 shows the targets set for hydrogen storage Hydrogen can be stored in the solid state by two means;
materials in vehicle based applications, recently updated physisorption and chemisorption. In physisorption, the hydrogen retains
by the Department of Energy (DoE) of the United States its molecular form and interacts with an adsorption centre or surface,
to be used in the freedom car. and high surface area materials are needed to physisorb hydrogen in
New targets (2009) large quantities. As the nature of the physisorption interaction is via
Storage parameter Units 2010 2015 Ultimate Van der Waals forces, low temperatures (<77 K) are usually required
System gravimetric capacity kWh/kg 1.5 1.8 2.5 to prevent thermal desoption of the hydrogen molecule from the
wt% H2 4.5 5.5 7.5 adsorption centre/surface. Here, the main technological challenge is
System volumetric capacity kWh/L 0.9 1.3 2.3
g H2/L 28 40 70 to increase the operating temperatures so that it approaches room
H2 delivery temp. (to FC) °C −40/85 −40/85 −40/95–105 temperature. Physisorption systems have the advantage of fast kinetics
Operating pressure (min./max.) MPa 0.5/1.2 0.5/1.2 0.3/1.2
Kinetics (g H2/s)/kW 0.02 0.02 0.02 for the hydrogen ad- and desorption (temperature controlled) with
Cost $/kWh net To be determined direct refuelling of such systems possible from hydrogen gas alone
(although at cryogenic temperatures).
temperature (0.0899 kg/m3), and very low boiling point (20.3 K) In the case of chemical hydrides, also known as complex hydrides,
these techniques require either very high pressures (>350 bar) hydrogen is stored by chemisorption, so called chemical storage. Here
or very low temperatures (22 K), respectively, to achieve high hydrogen is in its atomic form and it is chemically bound to other
volumetric and gravimetric storage densities. For example, elements, forming hydrides. The formation of these hydrides requires
hydrogen gas requires approximately 750 bar to reduce 4 Kg breaking the molecular dihydrogen bond, and the release of hydrogen
of hydrogen to 100 l at room temperature (40 g H2/l, the US require breaking the hydride bonds, both of which can require large
DOE 2015 target) and while liquid hydrogen has a volumetric energies. The advantage of chemical, or complex, hydrides, is that
density of 71 g H2/l, it requires cryogenic temperatures, with the they offer high gravimetric and volumetric densities. For example, the
concomitant energy penalty, to achieve liquefaction. The Japanese volumetric density of hydrogen in chemical hydrides can be two or more
New Energy and Industrial Technology Development Organization times that of liquid hydrogen (MgH2 ~130 g H2/l, LiBH4 ~120 g H2/l,
(NEDO) suggest 2010 targets for hybrid (high pressure and Mg2FeH6 ~148 g H2/l)1 at relatively low pressures with high gravimetric
reversible hydrogen storage material combined) storage tanks of densities hydrogen (MgH2 ~7.7 wt% H2, LiBH4 ~18.5 wt% H2/l,
5 Kg of H2 at 350 bar with an outer system volume of 100 l and a Mg2FeH6 ~5.5 wt% H2)1.
weight of 145 Kg, which is equivalent to approximately 3.5 wt% Fig. 1 shows a schematic representation of the current state of the
H2 and 50 g/l. art in hydrogen storage materials, highlighting the operating pressures

Fig. 1 Schematic representation of the temperature and pressure ranges for different practical hydrogen storage systems. The shaded area corresponds to the range of
pressures and temperatures of possible but non optimal conditions.

NOVEMBER 2009 | VOLUME 12 | NUMBER 11 55

REVIEW Neutron scattering and hydrogen storage
and temperatures of the various systems. The green area represents the
optimal operating conditions for the material and the shaded area the
possible use conditions. The best technologies at the present moment
lie in the circled areas. An excellent review of the field is given in
reference3.
Why using neutrons?
The nature of the interaction of neutrons with matter make neutrons
an ideal tool for studying the structural and dynamical properties
of materials. In particular, the sensitivity of neutrons to low atomic
number elements makes neutron scattering an ideal tool for the study
of hydrogen storage and battery materials. Neutrons are scattered by
the nuclei whereas photons (X-rays) are scattered by electrons and
because of their wavelength, thermal neutrons can simultaneously
measure structure and dynamics. In inelastic (spectroscopic) processes
the scattering conveys information on the dynamics across the
Brillouin zone, and it has no selection rules, unlike Raman and Infrared
spectroscopy (IR), making the assignment of the spectra relatively
straightforward. Neutron scattering is particularly suited to the study
of hydrogen atoms as the incoherent cross section of the hydrogen
nucleus is 80.26 barn, which is over 10 times larger than most other
common chemical elements4. This makes incoherent inelastic neutron
spectroscopy a very powerful tool to observe the dynamics of hydrogen
containing materials.
The spectroscopy of hydrogen
storage materials
The vibrational properties of solids and molecules are studied by
spectroscopic methods. Infrared (IR) and Raman spectroscopies are
well established optical techniques. Inelastic neutron scattering (INS)
spectroscopy is another method of obtaining vibrational spectra that
has the following advantages:
• INS spectroscopy is sensitive to the vibrations of hydrogen atoms;
whereas Raman and infrared are more sensitive to the motion
of heavier atoms (because of the larger number of electrons),
hydrogen due to its neutron cross section is ten times more visible
to INS than other elements;
• INS is not subject to optical selection rules. All vibrations are active
and, in principle, measurable;
• INS observations are not restricted to the centre of the Brillouin
zone (gamma point) as are the optical techniques;
• INS spectra are readily and accurately modelled: The intensities
are proportional to the concentration of elements in the sample
and their cross sections, the measured INS intensities relate
straightforwardly to the associated displacements of the scattering
atom and manipulation of backgrounds is straightforward;
• Neutrons penetrate deeply into materials and pass easily through
the walls of metal containers, aluminium or stainless steel, making
56 NOVEMBER 2009 | VOLUME 12 | NUMBER 11
neutrons ideal to measure bulk properties of samples within
controlled environments;
• INS spectrometers cover the whole range of the molecular vibration
spectra, 0-500 meV (0-4000 cm-1).
The scattering law determines the spectral intensity. For a given atom,
l, and a vibrational mode ν that involves a displacement vu1, the
scattering law is:
2 n
[(Q· v u1) ]
S(Q,ων)ln ∝ σl exp(–(Q · ∑ν vu1)2) (1)
n!
Where Q is the momentum transfer, ων is the vibrational frequency
of the ν mode, σl is the cross section of atom l and n is the final state
of the mode that has been excited5.
Rotational spectra of molecular Hydrogen
In the case of physisorption of hydrogen, neutrons can measure the
rotational transitions of the hydrogen molecule. The rotational spectra
of molecules lie in the low energy transfer region. Pure rotational
transitions are observed with INS around the elastic line. In particular,
due to the geometry of the hydrogen molecule, hydrogen rotational
transitions are easily measured using INS. The rotational energy levels
of the hydrogen molecule in vacuo are given by:
2
-h
EJ,M = J · (J + 1) · — = J · (J + 1) · Brot (2)
2I
where J and M are the rotational quantum numbers and I is the
moment of inertia. The hydrogen molecule has the lowest possible
moment of inertia; this translates as the highest rotational constant4,
Brot=7.35 meV (96 cm-1).
Because of the Pauli principle, the hydrogen molecule exists in
two different forms, para-hydrogen (paired nuclear spins) and ortho-
hydrogen (unpaired nuclear spins), the transitions between these
hydrogen species are usually forbidden in optical spectroscopy; when
excited with neutrons, transitions between species are allowed because
the scattering event causes a nuclear spin flip.
The rotational spectrum of solid parahydrogen, when measured with
an instrument like TOSCA6, consists of a very sharp rotational line at
2B or 14.7 meV (118 cm-1) corresponding to the J=1←0 rotational
transition and a series of recoil features. The changes in the position
of the rotational line of hydrogen, when interacting with different host
materials are used to determine the nature of the interaction potential.
Hydrogen deuteride (HD) has its rotational line at 11 meV7.
The relative cross sections for neutron scattering for the different
transitions was first presented by Young and Koppel8. A very
comprehensive review of the hydrogen molecule in the condensed
phase was given by Silvera in 19809. When interacting with a surface,
the rotational line position and shape are dependent of the nature of
 Neutron scattering and hydrogen storage
the interaction with the local environment. A simplified model for such
interaction consists of representing the interaction of the molecule
with the surface as a function of the polar angles that define the
orientation of the molecule with respect to the surface10. This model
was first used by Silvera11 to interpret the position of the rotational
line of para-hydrogen when adsorbed on γ-Al2O3.
Chemical/Complex hydrides
Metal hydrides have been the object of neutron studies since the
very beginning of the INS technique12-14. In 1996 Bogdanovic15
reported the use of additives that catalysed the hydrogenation/
dehydrogenation of NaAlH4. Since then a new impetus has been
given to the hydrogen storage field. A series of studies have been
performed on light metal chemical hydride systems using neutron
scattering16-23. Isotopic substitution has been used to identify the
mechanism of hydrogen storage and release as well as the effects
of the catalysts in the case of TiCl4/NaAlH420 and, recently, this
concept has been expanded to include identification of mechanisms
by Raman spectroscopy24 with complementary computer modelling
(Fig. 2). Here, comparison between experimental data and free energy
ab initio optimisation of the structure shows that the alkali metal
hydrides are better described by LDA instead of the most commonly
used GGA functions. Indeed, using LDA modelling it was possible to
accurately reproduce the structure and thermodynamics of the alkali
metal hydrides. The calculated and observed experimental data agreed
Fig. 2 The proposed mechanism for hydrogen transport for NaALH4.24 (© Royal Society of Chemistry).
extremely well with respects to structure, thermal expansion and
dynamics25,26.
Studies of the effects of nanostructuring and the introduction
of defects in the loading and release of hydrogen from MgH2 have
been studied by neutron scattering. The authors found that Nb and
V in very small quantities act as a catalyst during the hydrogenation
process. They observed the formation of sub-stoichiometric magnesium
hydride (MgH1+x, 0<x<1) and also a decrease in the temperature of
hydrogenation18. They attributed the improvement in the kinetics to
the presence of vacancies in the structure. INS studies of the same
material were consistent with this interpretation17,27. The power of
this technique was more recently demonstrated by Kathmann and
Schenter, who used INS to probe the effects of dihydrogen bonding on
the vibrational dynamics in the molecular crystal of ammonia borane,
a high weight percent (~19.5wt% H2) complex chemical hydride. They
showed that the thermal neutron energy loss spectra of 11B enriched
ammonia borane isotopomers ((BH3NH3), (BD3NH3) and (BH3ND3)
compared extremely well to the vibrational power spectrum calculated
using ab initio molecular dynamics in the 50-500 cm-1 region. A similar
approach has been used by Yvon et al., to investigate LaMg2PdH728 and
by Buchter et al., to investigate alkali metal tetrahydroborates22. INS
has also been used to confirm hydrogen uptake and to identify hydride
species by Jalowiecki-Duhamel et al. who showed CeMZNiXOY (M = Zr
or Al, Z = 0 or 0.5, 0 ≤ X ≤ 3) to be hydrogen reservoirs containing OH
and H– hydride species29.
NOVEMBER 2009 | VOLUME 12 | NUMBER 11 57
REVIEW Neutron scattering and hydrogen storage
Molecular hydrogen in porous materials
and surfaces
There are several general systems that are the focus of active
research in the field: metal organic frameworks (MOF), zeolites,
active carbons, nanotubes, polymers with intrinsic porosity (PIM)
and hydrogen clathrates. This is not an activated process so
reversibility and kinetics are not an issue. However the nature of the
interaction, (Van der Waal’s)30, is rather weak and there seems to
be a requirement for strong polarising centres so that the induced
polarisation of the hydrogen molecule can improve the strength of the
interaction.
Activated carbons nanotubes, nanohorns
and graphite
Following the initial interest generated by the report31 of more than
10 wt% hydrogen uptake on single wall carbon nanotubes (SWNT)
which proved to be irreproducible, a great deal of effort has been
devoted to the study of carbon based compounds (Fig. 3). The
interactions of the hydrogen molecule with carbon, graphite and
nanotubes have been extensively studied by INS30-37. The rotational
features indicate that the rotational barriers are very low and also
the adsorption energies are modest35,38. On carbon nanotubes, two
different experiments at different loadings produced very similar
spectra. In the first case, peaks at 13.5 and 14.7 meV (109 and
119 cm-1) were fitted to an area ratio of 2:1, implying a planar
orientation of the molecule35 while the second reported a 1:2 ratio,
but for the same peak positions38, implying a perpendicular orientation
to the surface. The peak positions in these spectra were critically
dependent on the chosen fitting procedures to analyse the spectra4.
Since these experiments were undertaken, better samples of higher
purities have been examined but the assignment is still unresolved
and the situation complicated by the confirmation of the presence
metallic impurities by the slow conversion of ortho-hydrogen into
para-hydrogen at low temperatures. On graphite the rotational line
of hydrogen is very slightly affected by the surface interaction and a
Fig. 3 Representation of hydrogen in carbon nanohorns.
58 NOVEMBER 2009 | VOLUME 12 | NUMBER 11
very small shift of 0.1 meV (0.8 cm-1)39 is observed. A high resolution
study of hydrogen adsorption on carbon nanohorns36 presented a 2:1
splitting of the rotational features broadened by the presence of the
“tip” of the structure.
On alkali metal-graphite intercalates, on the other hand, the
rotational line of hydrogen was extensively affected. Here the
rotational line produced features at 0.5, and 1.5 meV (4 and 12 cm-1),
and a further transition at 48.5 meV (391 cm-1). This last interaction
has been attributed to the electronic configuration of the hydrogen
molecule when interacting with the metal centre and a quantum
delocalisation effect40. It was concluded that the interaction between
H2 and the metal centre was strong enough to produce an appreciable
splitting of the rotational line.
Zeolites and metal oxides
Zeolites are porous, high surface area materials that find applications
in a variety of processes in the chemical industry. They are cheap to
produce, the world production of zeolites is in the order of millions
of tonnes and their properties can be tuned by changing the cations
that are usually present to charge-balance the structure. They are
also very strong materials, with the majority of zeolites stable at
high temperature, so the removal of water and contaminants may
be performed highly efficiently. They are also used in a variety of
hydrogenation reactions, giving the study of the interactions of
Fig. 4 The INS spectra of the molecular hydrogen in cation substituted X zeolite.

hydrogen with these materials a high significance with reference to
understanding of the catalytic behaviour of these materials. Although
it has been recognised long ago that zeolites are too heavy for use as
hydrogen storage media in transport applications30 even when the
strength of the host/H2 interaction is quite strong, they may find a use
in stationary or mass storage applications.
The rotational features of molecular hydrogen in zeolites are
markedly changed from those in free H2 – they range from 2 meV to
14.7 meV (Fig. 4). The nature of the interaction is electrostatic and
the induced dipole in the hydrogen molecule is responsible for these
shifts in the dihydrogen rotational spectra41-44. In particular studies
of the effect of the cationic substitution, the interaction energy has
been studied with vibrational spectroscopies42 and in particular with
INS41,44. It was found that the interaction energy increases linearly
with the polarising power of the cation substitution, as determined
by the vibrational frequencies of the centre of mass of the hydrogen
molecule when adsorbed in the material with different substitutions.
INS spectroscopy can provide unique access to the vibrations of the
hydrogen molecule as a whole against the metal centre.
Crystalline phases
There are few studies of hydrogen adsorption on the surfaces of pure
crystalline phases using INS. This is due to the relatively low sensitivity
of neutron scattering and thus for surface studies high surface area
materials are essential. However, it is possible to prepare45-47 MgO
particles with predominantly (100) facets and the authors have studied
the interaction of hydrogen with a very well defined surface. The
rotational line is not split, but instead it is located at 11.25 meV. As the
coverage increases the line shows a shoulder, but the centre of mass of
the whole peak remains fixed. The authors’ interpretation of the result
is a reorientation potential of the surface on the hydrogen molecule
that tends to put the molecule in a flat orientation.
Metal organic frameworks
Metal organic frameworks (MOF) are crystalline structures that are
formed by linking metal ions using organic ligands48. The structure is
an extended three dimensional network of channels and pores. These
materials are very versatile in their structures, shapes and sizes. These
materials also have very large surface areas, once the solvents used for
their production have been removed. The large surface areas and pore
volumes make MOFs very interesting candidate materials for hydrogen
storage, and consequently they are currently one of the most active
areas of materials research in energy storage49-59. In an early paper,
Rosi et al.60, used INS to determine the adsorption sites of hydrogen
in MOF-5. The authors concluded that the hydrogen molecule adsorbs
in two different sites, nominally next to the organic ring and on the
ZnO units. Much work has been devoted to determining the hydrogen
adsorption sites with INS by tracking the position of the rotational
line and using a sequence of different coverages61,62. Neutron powder
Neutron scattering and hydrogen storage
Fig. 5 The hydrogen positions in Cu3(BTC)2 as determined in64 The hydrogen
are represented as balls of different sizes according to their adsorption site.
diffraction was used to determine the adsorption sites of hydrogen
in Cu3(BTC)263-65 (Fig. 5). Six different adsorption sites for the D2
molecule were identified, that fill sequentially as the load increases,
and with the strongest interaction between the hydrogen molecule and
the metal centre. There is therefore a lot effort targeted at tuning the
interactions by substitution of the metal in these materials, a combined
INS and DFT study of the same system indicates that the anisotropy
of the potential energy surface on the adsorption site of hydrogen on
Cu is responsible for the very strong shift of the rotational line features
in this system66. The packing of hydrogen in some of these materials
achieves densities that surpass the density of liquid hydrogen67. A
comprehensive review of the field of MOFs and hydrogen storage can
be found in reference68
Ice clathrates
Ice clathrates are structures that consist of an extended network of
water molecules that form cavities that contain amounts of non-
polar gases (Fig. 6). The most common clathrates have carbon dioxide
and methane as guest molecules, although hydrogen can also be
a guest molecule in a clathrate69. The nature of the motion of the
hydrogen molecule in a clathrate has been studied with INS and the
vibration and rotation of the hydrogen molecule can be seen in the
spectra (Fig. 7). The vibration and rotation of the molecule has been
deconvoluted in these materials using high resolution spectroscopy
and the use of different para-hydrogen/ortho-hydrogen ratios in
clathrate occluded dihydrogen molecules70,71. With the spectroscopic
information on the molecular hydrogen vibrations it is possible to
calculate the potential energy surface that the hydrogen molecule
experiences inside the cavity. The spectra presented by Ulivi70,71
were measured on clathrates that have the large cages filled with
NOVEMBER 2009 | VOLUME 12 | NUMBER 11 59
REVIEW Neutron scattering and hydrogen storage
Fig. 6 The structure of the sII ice clathrate. On the right, a view of the large cage
from two angles, and a depiction of the small cage at the bottom right.
tetrahydrofuran instead of hydrogen making the material easier to
prepare, but reducing its hydrogen content.
Catalysis and fuel cells
Catalysis is the key to both life and lifestyle. There are fundamental
catalytic processes related to fuels and energy, emissions, polymers
and plastics, life, health and food. Catalysts and catalytic processes
have been used for a long time in industry, however, in many cases,
we lack an understanding of the operation of the catalyst and the
impact of catalysis in hydrogen storage and fuel cells cannot be
ignored.
INS investigation of catalysts has been undertaken for over 30
years72-75. INS is not a surface sensitive technique since the neutrons
Fig. 7 The INS spectra of hydrogen in an ice clathrate showing the spectrum de-convoluted into the para- and ortho-hydrogen contributions70,71.
60 NOVEMBER 2009 | VOLUME 12 | NUMBER 11
penetrate deep into matter and so to obtain high sensitivity, a high
surface to bulk ratio is needed as well as an adsorbent that contains
hydrogen. In that respect, INS is simultaneously a bulk and a surface
science technique, with a sample size of, usually, 10-150 g. In the
case of industrial samples, the large amount of material required
is not problematic and also acts to average effects that happen at
a microscopic level. A variety of systems have been studied using
neutrons, for a comprehensive review on the applications of neutron
scattering to catalysis see75.
Fuel cell catalysts have been investigated using INS to characterise
hydrogen adsorptions sites and the spillover phenomena32,39,76,77. Fuel
cells under realistic operation have also been studied using neutron
radiography and tomography, studies to visualise the water distribution
and flow on an operating fuel cell are given in references78-81.
Conclusion
Inelastic neutron scattering has proved itself an exemplary tool for
investigating hydrogen storage materials, providing information on
host-hydrogen interaction, molecular dynamics and the nature of
the hydrogen containing species. A great many different hydrogen
storage systems may be studied by inelastic neutron scattering,
and the technique is ideally suited for these materials as it provides
direct information on the nature of the interaction of hydrogen with
matter. The combination of inelastic neutron scattering and Density
Functional Theory modelling methods to understand the fundamental
dynamic processes of these materials has been well established.
More recent studies have begun to focus on complex hydrides and/
or host/hydrogen systems whose functional properties approach those
required for commercial application. Future studies will shed light on
the mechanisms of reaction, dehydrogenation and rehydrogenation, so
that the operating regimes for these hydrogen storage materials can

be tailored to fall within the required targets for these applications.
Furthermore, developments in the method of data collection will permit
variable temperature measurements to be performed and thus allow the
processes of hydrogenation and dehydrogenation monitored directly.
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NOVEMBER 2009 | VOLUME 12 | NUMBER 11 61
OPINION

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.
Sanjeev Mukerjeea, V. Renugopalakrishnanb, Bernardo Barbiellinia, Sowmya Viswanathanc, Michael Chind, and P. Somasundarand
aNortheastern University, Boston MA 02115, USA
bChildren’s Hospital, Harvard Medical School, Boston, MA 02115, USA
cNewton-Wellesley Hospital/Partners Healthcare System, Newton, MA 02462, USA
dLangmuir Center for Colloids and Interfaces, Columbia University, New York, NY 10027, USA

A topical symposium of current global interest
entitled “Materials Challenges for Clean Energy
in the New Millennium” was held on April 29 at
Northeastern University and inaugurated by the
former President of India, Dr. A. P. J. Abdul Kalam,
a visionary engineer. The event was co-sponsored
by Harvard School of Engineering and Applied
Sciences. The symposium aimed to formulate
cutting edge solutions for challenges facing the
next generation clean energy technologies.
As the bio-nano interface holds most promise
for benign technologies, the program featured
distinguished visionaries working at this
scientific frontier in terms of materials design
and manipulation at the atomic scale. The
common goal was to develop novel materials and
techniques capable of satisfying the demands
for clean energy in the new millennium. Exciting
solutions based on improved catalysts, green
membranes, superconductivity, hybrid technology
for batteries, polymers and photosensitive proteins
for robust solar cells were considered by the
speakers. With these in mind, Professor George
Whitesides (Harvard) and Mildred Dresselhaus
(MIT) provided overarching views of the clean
energy generation landscape. While Professor
Whitesides listed advancements in solar conversion
and improvements in catalysis as the keys for
the future and discussed the need to explore new
chemical pathways for CO2 conversion to “clean”
hydrocarbon fuel. Professor Dresselhaus’ illustrated
the engineering of materials for clean energy using
bottom up approaches; For instance, nano-building
blocks can be used to optimize thermo-electric
devices, solar cells, fuel cells and batteries.
Solar energy was a particular focus of the
symposium, as it has long been an attractive source
of clean and abundantly renewable energy, despite
only representing a tiny fraction of the produced
energy mostly due to economical reasons.
Fortunately, the advent of new nanomaterials
is expected to significantly reduce the costs of
solar energy production. It was also noted that,
atomic level engineering can be used effectively
on surfaces for catalysis or in bulk materials for
H or Li intercalation. As far as transportation is
concerned, recent progress in superconductivity
was noted to provide solutions both for mitigating
transmission losses for more compact engines.
These breakthroughs in tandem with progress in Li
intercalated materials are pushing the cutting edge
of plug-in hybrid technology in transportation.
Professor Sanjeev Mukerjee (Northeastern
University) discussed ways to design new materials
for hybrid flow through batteries enabling safer
storage devices with greater energy densities
and rate capability. Based upon advances in
nanotechnology, special materials could be tailored
for a transition to non-noble metal electro catalysis
in conventional low and medium temperature acid
and alkaline exchange membrane fuel cells. The
need for nanofabricated electrochemical interfaces
was also emphasized for improving transport and
charge transfer efficiencies.
Professor Charlie Lieber (Harvard) showed how
advances in the synthesis and the doping of
semiconductor nanowires make this class of
nanostructures a powerful platform for testing
fundamental concepts and limits of photovoltaics
down to the level of single nanowires. His
investigations have demonstrated very high short-

62 NOVEMBER 2009 | VOLUME 12 | NUMBER 11


Partial list of speakers at symposium
circuit current densities resulting from efficient
carrier collection in radial or coaxial p-i-n structures
and robust photovoltaic elements even under
highly concentrated solar illumination.
Professor Shriram Ramanathan (Harvard)
introduced the science of ultra-thin oxides,
particularly tuning microstructure-electrochemical
property relationships in fluorite-structured
systems. By utilizing oxide superlattices and
by controlling the oxygen partial pressure,
novel energy materials can be synthesized. The
fabrication of on-chip solid oxide fuel cells utilizing
ultra-thin oxide films for high performance portable
energy was subsequently explained in detail.
Dr. Gilles Dennler (Konarka Technologies Inc.,
Lowell, MA) reported encouraging progress on
conjugated polymer-fullerene bulk-heterojunction
solar cells performed in collaboration with Professor
Alan J. Heeger (UC Santa Barbara). The new
Konarka’s organic photovoltaic cells are expected to
soon be into commercial production.
Professor Robert Blankenship (Washington
University in St. Louis) demonstrated how the
photosynthetic membranes can be considered as
natural bio-energy conversion devices. He listed
several molecular complexes that serve as antennas
by absorbing photons and delivering the energy to
the reaction centers.
Photosynthesis is a collection of the most advanced
and efficient systems Nature has crafted to convert
solar energy into an electrical potential and again
into chemical compounds for energy storage.
Thus, Bio-solar cell and bio-fuel cell represent
the emerging frontier in green energy sources.
Professor Eric Diau and co-workers (National Chiao
Tung University, Taiwan) have reported a detailed
study on excited state dynamics of porphyrins
sensitized solar cells with various linker lengths.
NOVEMBER 2009 | VOLUME 12 | NUMBER 11
OPINION
Professor Venkatesan Renugopalakrishnan (National
University of Singapore, Harvard, and Northeastern
University) reported advances in the feasibility
of bacteriorhodopsin as bio-photosensitizer in
excitonic solar cell. His Lab has engineered mutants
of bacteriorhodopsin to enhance thermo-stability
and to favor the charge separation when the
photons are absorbed. Professor Gerald Audette
(York University Toronto) discussed bio-fuel cells
based on Glucose Oxidase (GOx). These devices
are assembled with anodes from cross-linked GOx
clusters localized on multiwalled carbon nanotubes.
In an inclusive approach to the state of nano and
interfacial science in regards to environmentally
responsible energy recovery, Professor Somasundaran
(Columbia) delivered a comprehensive overview on
green nanostructures for enhanced energy recovery.
A consequential outcome of correlation between
structure and performance makes the importance
of naturo-structures in terms of both orientation
and conformation at the nanolevel that will prove
powerful in enhancing the efficiency of energy
extraction, whether from coal or oil or nuclear or
solar sources.
It is clear that as natural models are
environmentally benign, it is incumbent on us
to explore development of such structures for
designing biosolar cells. Evidently, accurate
probing of all the above phenomena requires us
to have new and improved equipment to explore
phenomena in the super thin fast world. As an
example, application of scanning electrochemical
microscope in the discovery of photo catalysis for
was illustrated by Professor Allen J. Bard (University
of Texas at Austin).
The best processes will result from a confluence of
ultra small science with ultrafast engineering. It was
clear during the meeting that the future is indeed
promising but challenges are enormous, warranting
the attention of the best minds in the world and
collaboration amongst them.
For further reading
www.northeastern.edu/nucret/
www.northeastern.edu/bionano/
63
EVENTS DIARY
FORTHCOMING EVENTS
3 – 8 January 2010
IEEE International NanoElectronics
Conference (INEC) 2010
Hong Kong (PR China)
INEC2010 will feature plenary and
invited talks by famous scientists
in nanofabrication, nanoelectronics,
nanophotonics, and nanobiology. A
special symposium on nanoscience and
nanotechnology in China featuring all
invited talks by academicians of the
Chinese Academy of Sciences, Chinese
Academy of Engineering, and Academia
Sinica will be held during the conference.
http://www.cityu.edu.hk/ieeeinec/index.
htm
10 – 14 January 2010
37th Conference on the Physics and
Chemistry of Surfaces and Interfaces
(PCSI-37)
Santa Fe – New Mexico – USA
The 37th Conference on the Physics and
Chemistry of Surfaces and Interfaces
(PCSI-37) will be held at Hotel La
Fonda in Santa Fe, New Mexico from
Sunday at 3:00p.m., January 10, through
Thursday noon, January 14. The annual
PCSI conference is devoted to achieving
a fundamental understanding of the
physical, chemical, biological, structural,
optical, magnetic and electrical
properties of surfaces and interfaces.
http://www.pcsiconference.org/
20 – 22 January 2010
Electronic Materials and Applications
2010
Orlando – FL – USA
Jointly programmed by the Electronics
Division and Basic Science Division of
ACerS, this is the first in a series of
annual meetings. The 2010 focus is on
electronic ceramics for energy storage
and conversion applications and the
complementary fundamental science
issues
http://ceramics.org/electronic-materials-
and-applications-2010/
23 – 28 January 2010
SPIE Photonics West
San Francisco – USA
Experience SPIE Photonics West—the
worlds leading photonics, laser, and
biomedical optics event
http://spie.org/x2584.xml
For further information please visit www.materialstoday.com/events
64 NOVEMBER 2009 | VOLUME 12 | NUMBER 11
24 – 29 January 2010
34th International Conference and
Exposition on Advanced Ceramics and
Composites (ICACC)
Daytona Beach – FL – USA
This conference showcases cutting-edge
research and product developments in
advanced ceramics, armor ceramics,
solid oxide fuel cells, ceramic coatings,
bioceramics and more. Investigate the
11 symposia and 4 focused sessions
planned for 2010.
http://ceramics.org/34th-international-
conference-exposition-on-advanced-
ceramics-composites/
01 – 05 February 2010
Introduction to Physical Metallurgy
University of Surrey – Surrey – UK
The course aims to provide a general
introduction to the field of Physical
Metallurgy. It covers phase diagrams,
transformation diagrams and the
associated thermodynamics, diffusion,
liquid-solid transformations, ferrous and
non-ferrous materials and cold work,
recovery and recrystallisation.
http://portal.surrey.ac.uk/portal/page?_
pageid=822,1938865&_dad=portal&_
schema=PORTAL
8 – 9 February 2010
RIEG course on the Behaviour of
Rubber Materials
Kolnmessa – Cologne – Germany
This course is designed specifically
to give a detailed overview of all the
core concepts involved in the design of
rubber products.
http://www.iom3.org/events/
short-course-behaviour-rubber-
materials?c=2822
10 February 2010 – One day event
RIEG conference on Advanced
Analytical Techniques in Elastomers
Kolnmessa, Cologne, Germany
This session concentrates on new and
emerging trends in the rubber research
community.
http://www.iom3.org/events/rieg-
session-tiretech-conference?c=2822
15 – 19 February 2010
Polymers: Science, Engineering and
Applications
University of Surrey – Surrey – UK
This course combines a comprehensive
study of the science and engineering
of polymers with an up-to-date
appreciation of the development and
application of polymers in traditional
and new areas. The course starts with
a good insight into the physical and
chemical structure and the various
types of polymers. Polymer synthesis,
chemical and physical processing
diary
techniques and manufacturing Each month we publish brief
technologies are presented for the details of current and forthcom-
development of polymer structures and ing meetings. The forthcoming
the manufacturing of polymer products meetings are listed for a 3
for various applications. months period of time starting
3 months after the current
http://portal.surrey.ac.uk/portal/page?_ issue, leaving sufficient time
pageid=822,2436682&_dad=portal&_ for registration. This list is not
exhaustive.
schema=PORTAL
If you are organizing a future
conference or workshop and
21 – 25 February 2010 would like to have it listed in
Materials Challenges in Alternative & Materials Today please contact
Renewable Energy 2010 Jonathan Agbenyega –
Cocoa Beach – Florida – USA j.agbenye@elsevier.com.
Events Materials Today has a
Designed to bring together leaders in contra deal with and that are
materials science and energy, Materials relevant to the current issue of
Challenges 2010 aims to facilitate the magazine are listed in the
information sharing on the latest box below.
developments involving materials
for alternative and renewable energy If, as an organizer, you would
systems like to discuss a contra deal,
please contact Francesca Webb
http://ceramics.org/materials-challenges- – f.webb@elsevier.com
in-alternative-renewable-energy-
sources-2010/
28 February – 5 March 2010
Pittcon 2010
Orlando – Florida – USA
Pittcon 2010 will again offer the latest
advances in laboratory instrumentation,
supplies and services; comprehensive
solutions for research problems; new
methodologies and techniques for
improved productivity; and a wide range
of educational opportunities.
http://www.pittcon.org/president/
PC10welcome.html
9 – 12 March 2010
2nd NanoImpactNet Conference
Lausanne – Switzerland
This training workshop is aimed at PhD-
students, postdocs and early-career
scientists and provides training on
handling protocols, choices of control
materials, dispersion procedures, and
hazard evaluation procedures.
http://www.nanoimpactnet.eu/object_
class/nano_lausanne2010conference.html
The Institut national de la recherche scientifique, a university institution dedicated to research and postgraduate studies,
seeks to fill a tenure track position in Nanobiotechnology, associated with a Tier 2 Canada Research Chair, at its Énergie
Matériaux Télécommunications Centre (for information on the Canada Research Chairs program, visit: www.chairs.gc.ca). A Tier 2
Chair is intended for exceptional emerging researchers who have the potential to become leaders in their field. This position is
incorporated within an environment where about forty professors-researchers undertake leading-edge research and teaching in
diverse fields of energy, materials and telecommunications.
One of our main axes of strategic development is in the field of nanobiophotonics, broadly defined as the synthesis, processing
and imaging/characterization of nanosystems relevant to biology, including, but not limited to applications in health and the
environment. Research topics of interest for this position may include the use of nanomaterials and processes in the broad areas
of infections and cancer, both diagnosis and therapy, gene therapy, tissue repair/regeneration/engineering, the modification and
characterization of biocompatible materials, advanced imaging of molecular systems from simple biomolecules to viruses to
living cells (including animal studies in vivo).
The Institute is located in Varennes, on the South Shore of Montreal. More information is available on the web site: www.emt.inrs.ca.

PROFESSOR-RESEARCHER
NANOBIOTECHNOLOGY
(Tenure Track – Tier 2 Canada Research Chair)
The candidate should have:
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THREEREFEREESBEFOREJanuary 31, 2010INDICATINGCOMPETITIONDS 09-06 to:
Dr. Jean Claude Kieffer, Director
Centre Énergie Matériaux Télécommunications
1650, Lionel-Boulet Blvd.
Varennes (Québec) J3K 1S2, Canada
kieffer@emt.inrs.ca
).23ISCOMMITTEDTOEQUITYINEMPLOYMENTANDDIVERSITY4HE)NSTITUTEWELCOMESAPPLICATIONSFROMINDIGENOUSPEOPLEVISIBLEMINORITIESETHNICMINORITIESPERSONSWITHDISABILITIESWOMENPERSONSOFMINORITY
SEXUALORIENTATIONSANDGENDERIDENTITIESANDOTHERWHOMAYCONTRIBUTETOFURTHERDIVERSIFICATION

W W W. I N R S . C A

Centre - Eau Terre Environnement

Centre - Énergie Matériaux Télécommunications
Centre - INRS−Institut Armand-Frappier
Centre - Urbanisation Culture Société
 You asked. We listened.
Ultrahigh Resolution Analytical Performance

Ultralow kV EDS/WDS
Uncoated EDS map of
stretched TiO2 in FeOx
polypropylene with <100nm
spatial resolution
30,000x

LABe EBSD
1-3 nm twinning Orientation
in mineral BSE map of Ni alloy
image

STEM CL
CNT with Quartz and
1-3 nm Pt zinc oxide
nanoparticles

Another
Seeing is believing! Extreme
Contact salesinfo@jeol.com to arrange a demo. Imaging
For more information or to view a brochure Solution
visit www.jeolusa.com/7600F. JSM-7600F
All magnifications as printed at 4 x 5 in.
KFPM
Stability • Performance • Productivity
www.jeolusa.com • salesinfo@jeol.com
978-535-5900