materials

Article
In Situ TEM Multi-Beam Ion Irradiation as
a Technique for Elucidating Synergistic
Radiation Effects
Caitlin Anne Taylor 1,2 , Daniel Charles Bufford 1,3 , Brittany Rana Muntifering 1,2 , David Senor 4 ,
Mackenzie Steckbeck 1 , Justin Davis 1 , Barney Doyle 1 , Daniel Buller 1 and
Khalid Mikhiel Hattar 1, * ID
1 Radiation Solid Interactions, Sandia National Laboratories, Albuquerque, NM 87185, USA;
ctaylo@sandia.gov (C.A.T.); dcbuffo@sandia.gov (D.C.B.); brmunti@sandia.gov (B.R.M.);
mackenzie.steckbeck@ttu.edu (M.S.); davisj@unm.edu (J.D.); bldoyle@sandia.gov (B.D.);
dlbulle@sandia.gov (D.B.)
2 Analytical Technologies, Sandia National Laboratories, Albuquerque, NM 87185, USA
3 Energetics Characterization, Sandia National Laboratories, Albuquerque, NM 87185, USA
4 Energy and Environment, Pacific Northwest National Laboratory, Richland, WA 99354, USA;
David.Senor@pnnl.gov
* Correspondence: khattar@sandia.gov; Tel.: +1-505-845-9859

Received: 16 August 2017; Accepted: 27 September 2017; Published: 29 September 2017

Abstract: Materials designed for nuclear reactors undergo microstructural changes resulting
from a combination of several environmental factors, including neutron irradiation damage, gas
accumulation and elevated temperatures. Typical ion beam irradiation experiments designed for
simulating a neutron irradiation environment involve irradiating the sample with a single ion beam
and subsequent characterization of the resulting microstructure, often by transmission electron
microscopy (TEM). This method does not allow for examination of microstructural effects due
to simultaneous gas accumulation and displacement cascade damage, which occurs in a reactor.
Sandia’s in situ ion irradiation TEM (I3 TEM) offers the unique ability to observe microstructural
changes due to irradiation damage caused by concurrent multi-beam ion irradiation in real time.
This allows for time-dependent microstructure analysis. A plethora of additional in situ stages can
be coupled with these experiments, e.g., for more accurately simulating defect kinetics at elevated
reactor temperatures. This work outlines experiments showing synergistic effects in Au using in situ
ion irradiation with various combinations of helium, deuterium and Au ions, as well as some initial
work on materials utilized in tritium-producing burnable absorber rods (TPBARs): zirconium alloys
and LiAlO2 .

Keywords: ion irradiation; triple beam; in situ TEM; synergistic effects; ion implantation;
helium bubble; radiation effects

1. Introduction
The materials design process for advanced nuclear fission and fusion reactors requires
understanding material behavior in extreme environments. Structural reactor materials must satisfy
standard materials design criteria based on mechanical properties, thermal creep, cyclic fatigue and
combined creep-fatigue, as well as adequate resistance to radiation damage and chemical degradation
(e.g., corrosion and stress corrosion cracking) [1]. Material response to radiation damage is typically
investigated by either placing samples in a test reactor, or by utilizing ion irradiation to simulate
neutron damage. Ion irradiation offers the advantage of more rapid damage accumulation (which
often reduces experimental times from months or years to hours or days) and often does not leave

Materials 2017, 10, 1148; doi:10.3390/ma10101148 www.mdpi.com/journal/materials

Materials 2017, 10, 1148 2 of 20

samples with residual radioactivity. Most ion accelerator facilities offer the capability of irradiating
with a range of ion species and energies that simulate the defect cascades produced by neutron
irradiation, or implanting with lower energy gas ions to simulate bubble formation. These experiments
neglect the concurrent effect of defect-gas atom interaction that occurs in a real reactor irradiation
environment. Some facilities, e.g., the Joint Accelerators for Nano-science and Nuclear Simulation
(JANNUS) [2] and the Takasaki Ion Accelerators for Advanced Radiation Application (TIARA) [3],
have developed multi-beam irradiation capabilities, which allow for the exploration of these synergistic
effects. The combined effects can be striking; for instance, Tanaka et al. demonstrated minimal swelling
in Fe-Cr alloys when irradiated with concurrent Fe/He and Fe/H beams, but more than an order of
magnitude increase in swelling and void formation during irradiation with all three species at once [4].
While clearly important, experiments that elucidate these effects remain difficult to realize in practice,
in terms of both the necessary irradiation and microstructural characterization capabilities.
Early electron microscopists identified in situ TEM as a tool that would elucidate the role of crystal
defects, give accurate kinetic measurements of reaction rates and provide evidence for the mechanisms
of dynamic processes through direct observation [5]. Electron beam irradiation effects quickly became
one of the first topics studied within in situ TEM due to the electron beam damage innately experienced
by materials inside the microscope once the knock-on energy is exceeded. Depending on the threshold
displacement energy of atoms inside the material, even a 200 keV electron beam can produce Frenkel
pair damage in some materials. High voltage electron microscopes facilitated the creation of point
defects and the subsequent direct observation of their effects. Ion irradiation performed in situ in the
TEM allowed for direct observation of more complicated radiation effects. In situ ion irradiation in
the TEM quickly became an important technique and has been thoroughly reviewed elsewhere [6–9].
The first in situ ion irradiations were performed unintentionally in 1961 due to the emission of O− ions
from a contaminated tungsten electron gun filament [10] and were initially employed intentionally
in 1966 by using O− ion beams generated by BaCo3 - or SrCo3 -coated filaments inside the electron
microscope [11]. Researchers at Harwell [12] first generated a heavy-ion beam by connecting an ion
accelerator to an electron microscope. Similar facilities were created shortly after by researchers at the
University of Virginia, University of Tokyo, Argonne National Laboratory, and many others.
Today, the in situ ion irradiation TEM (I3 TEM) [13] at Sandia National Laboratories combines
single, double and triple ion beam irradiation with the real-time visualization power of in situ TEM.
The ability to irradiate with two or three ion beams simultaneously allows for exploration of synergistic
effects between He gas accumulation, cascade damage, H isotopes and temperature, making the I3 TEM
a unique facility for investigating radiation effects in materials. This work presents initial results of in
situ triple ion irradiation experiments on a variety of materials, beginning with the discussion of the
accelerator beam line optics required to guide three ions of a vastly different mass energy product into
the TEM through a single port, then discussing triple ion beam irradiations in a model face-centered
cubic (FCC) system, Au, followed by initial results of triple ion irradiation in materials utilized in
tritium-producing burnable absorber rods (TPBARs), zirconium alloys and LiAlO2 .

2. Materials and Methods

2.1. Accelerator Beam Line Design

The I3 TEM facility, discussed in detail in Hattar et al. [13], consists of a JEOL 2100(HT) LaB6
microscope (JEOL USA, Peabody, MA, USA), connected to an accelerator beam line capable of receiving
beams from two accelerators: a 10-kV Colutron G-1 ion accelerator (Colutron Research Corporation,
Longmont, CO, USA) and a 6-MV Van de Graaff-Pelletron Tandem Accelerator (High Voltage
Engineering Corporation, Burlington, MA, USA). Ion beams from the Colutron are accelerated to a
maximum energy of 10q keV, where q is the ion charge state, and bent 20◦ toward the microscope with
an electromagnet. The ion beam from the Tandem enters the beam line along the TEM axis (Figure 1).
Most typical Colutron beams are keV energy 4 He+ and 2 D2 + . These beams simulate the effects of
Materials Materials
2017, 10,2017,
114810, 1148 3 of 19 3 of 20

the TEM axis (Figure 1). Most typical Colutron beams are keV energy 4He+ and 2D2+. These beams
simulate thetransmutation
neutron-induced effects of neutron-induced transmutation
through (n,α) and (n,p)through
nuclear(n,α) and (n,p)
reactions nuclear reactions
in materials used inin nuclear
reactors.materials
Deuteriumused ions
in nuclear
werereactors.
selectedDeuterium
instead ofions were selected
protium to matchinstead of protium
the mass energyto match
productthe of 4 He+
mass energy product of 4He+ and to ease identification in post-mortem chemical analysis. By
and to ease identification in post-mortem chemical analysis. By matching the beam rigidity, both
matching the beam rigidity, both beams are steered identically by the Colutron bending magnet and
beams are
TEM steered
lenses, identically by the
permitting both 4He+Colutron
and 2D2+ tobending magnet
be produced and
by the TEM
same lenses,and
Colutron permitting both 4 He+
bent into the
and 2 D2TEM
+ to be produced by the same Colutron and bent into the TEM simultaneously.
simultaneously.

Figure 1. Diagrams showing the I3TEM facility, starting with (a) an image of the beam line, marked
Figure 1. Diagrams
with arrows to showing the I3 TEM
show the Colutron facility,
magnet, Tandemstarting with (a)
electrostatic an image
steerers and theof the beam
original line,ofmarked
locations
with arrows to show
the Colutron andthe Colutron
Tandem magnet,
beams; Tandem
(b) a Solid Works electrostatic
drawing of thesteerers
beam line and theclearly
in (a), original locations of
showing
the Colutron
the Colutron and Tandem
and Tandem beam(b)
beams; lines joiningWorks
a Solid at the Colutron
drawing magnet;
of the(c)beam
the Tandem
line inbeam trajectory
(a), clearly showing
through
the Colutron theTandem
and Colutron beam
magnet; and joining
lines (d) the Colutron beam trajectory
at the Colutron magnet; through theTandem
(c) the Colutronbeam
magnet,
trajectory
indicated clearly with dashed yellow lines.
through the Colutron magnet; and (d) the Colutron beam trajectory through the Colutron magnet,
indicated
Theclearly
bendingwith dashed yellow
electromagnet lines.
of the Colutron slightly deflects the Tandem beam, in some cases
causing the beam to miss the TEM sample. To alleviate this problem, steering magnets installed
The bending
before electromagnet
the Colutron of the are
bending magnet Colutron slightly
used to offset deflects the
the trajectory of theTandem
Tandembeam, in some
beam from the cases
causingaxis
the of
beam to miss magnet
the Colutron the TEM sample.
and To to
ultimately alleviate thisions
deflect the problem, steeringofmagnets
in the direction installed
the TEM target. In before
the Colutron
additionbending
to thesemagnet are used
two magnets, theretoisoffset the trajectory
a strong, of the Tandem
constant magnetic field aroundbeam thefrom the axis of
samples
produced
the Colutron by theand
magnet objective lenses inside
ultimately the TEM,
to deflect the which
ions inaffects the trajectory
the direction of of
thetheTEM
light,target.
low energy
In addition
Colutron beam. The Colutron beam must therefore be offset from the axis of the TEM such that the
to these two magnets, there is a strong, constant magnetic field around the samples produced by the
circular trajectory of ions in this magnetic field directs them to the center of the sample. Figure 1c
objective lenses inside the TEM, which affects the trajectory of the light, low energy Colutron beam.
shows the trajectory of ion beams produced by the Tandem accelerator through the Tandem steering
The Colutron
magnetsbeam must
and the therefore
Colutron be and
magnet, offset from
Figure 1dthe axis
shows theoftrajectory
the TEM of such that produced
ion beams the circular trajectory
by the
of ions in this magnetic
Colutron through thefield directs
Colutron them to the center of the sample. Figure 1c shows the trajectory
magnet.
of ion beams produced by the Tandem accelerator through the Tandem steering magnets and the
2.2. Characterization of the He + D Beam
Colutron magnet, and Figure 1d shows the trajectory of ion beams produced by the Colutron through
the Colutron Experiments
magnet. were performed to quantify the He/D ratio coming from the single Colutron ion
beam. Beam current was estimated during experiments from a Faraday cup biased to 300 V to
suppress electron
2.2. Characterization emission.
of the He + DImplantations
Beam of 1 × 1014, 6 × 1014, 3 × 1015, 3 × 1016, 6 × 1016, 1 × 1017 and
1 × 1018 ions/cm2 were performed into silicon wafers using the ex situ implantation chamber seen in
Experiments were performed to quantify the He/D ratio coming from the single Colutron ion
beam. Beam current was estimated during experiments from a Faraday cup biased to 300 V to suppress
electron emission. Implantations of 1 × 1014 , 6 × 1014 , 3 × 1015 , 3 × 1016 , 6 × 1016 , 1 × 1017 and
1 × 1018 ions/cm2 were performed into silicon wafers using the ex situ implantation chamber seen
in Figure 1a,b to investigate the composition of the He + D beam from the Colutron. Elastic recoil
detection (ERD) [14] experiments were performed with a 24 MeV Si4+ probe beam. The sample was
tilted 15◦ towards the detector, and a 30◦ recoil angle was utilized. A 13.5-m Mylar range foil was
 Materials 2017, 10, 1148 4 of 19

Figure 1a,b to investigate the composition of the He + D beam from the Colutron. Elastic
Materials 2017, 10, 1148
recoil
4 of 20
detection (ERD) [14] experiments were performed with a 24 MeV Si probe beam. The sample was
4+

tilted 15° towards the detector, and a 30° recoil angle was utilized. A 13.5-m Mylar range foil was
positioned
positioned in front of the
in front detector
of the detectorto screen incoming
to screen incomingSi recoils. A known
Si recoils. A known standard
standardof SiN implanted
of SiN implanted
with
with H was utilized for quantification purposes. Results from the ERD experiments appear2. in
H was utilized for quantification purposes. Results from the ERD experiments appear in Figure
ForFigure
clarity,
2. the × 1014the
For 6clarity, 6 ×610×14 10
and and16 ions/cm 2 samples
6 × 1016 ions/cm have have
2 samples been been
omitted fromfrom
omitted Panel (a). (a).
Panel Peaks
Peaks
arising from
arising fromO and
O andH present at the
H present sample
at the samplesurfaces were
surfaces identified
were consistently,
identified consistently,andand
peaks
peaksforfor
thethe
D and
D andHeHe indicate
indicatethat both
that bothspecies
speciesreached
reachedthe thesample
samplein in the
the measured
measured area. Quantification
Quantificationofofthe
theresults
resultsrevealed
revealed that
that concentrations were were approximately
approximatelyone oneorder
orderofofmagnitude
magnitude lower
lowerthanthanthethe
nominal fluences estimated from the Faraday cup measurement and that the ratio of
nominal fluences estimated from the Faraday cup measurement and that the ratio of D to He remained D to He remained
around
around1.8.1.8.

Figure 2. Elastic
Figure recoil
2. Elastic detection
recoil (ERD)
detection results
(ERD) from
results He He
from + D+ implantations
D implantationsintointo
Si wafers, showing
Si wafers, showing
labeled peaks for select fluences in (a) and the measured areal density as a function of ion implantation
labeled peaks for select fluences in (a) and the measured areal density as a function of ion implantation
fluence in (b).
fluence in (b).Most
Mosterror
errorbars
barsarearesmaller
smallerthan
thanthe
thedata
datapoints
pointsinin (b). Note that
(b). Note that the
the scales
scalesare
arelog
log(vertical)
(vertical)in
in(a)
(a)and
andlog-log
log-login
in (b).
(b).

2.3.2.3.
Experimental Details
Experimental Details
A variety
A variety of TEM
of TEM stages
stagesareareavailable
available forfor useuse
at the
at theSandia
SandiaI3 TEM
I3TEM facility, enabling
facility, enabling studies
studiesof of
synergy between ion irradiation damage and environmental effects. The angle of tilt (around +30 ◦ in x)
synergy between ion irradiation damage and environmental effects. The angle of tilt (around +30° in x)
required
required for the
for ion
thebeam ion tobeamhit thetosample inside
hit the each holder
sample insidehaseachbeen holder
previously hasdetermined [13].
been previously
Iondetermined
beams are aligned
[13]. Ion ontobeamsthe sample stageonto
are aligned with thea piece of quartz
sample stage attached
with a piece to a JEOL single-tilt
of quartz stage,
attached to a
as described in Hattar et al. [13], with each beam aligned individually in
JEOL single-tilt stage, as described in Hattar et al. [13], with each beam aligned individually in the the case of double and triple
ioncase
irradiation
of double experiments.
and triple Ion ionand electronexperiments.
irradiation beam spots are Ionburned into tape
and electron to confirm
beam spots aretheir overlap
burned into
prior
tapeto to
starting
confirm the their
experiment.
overlapThe beam
prior area used
to starting thetoexperiment.
calculate theThe totalbeamfluenceareais estimated from thethe
used to calculate
burn spot
total area. In
fluence this work, from
is estimated roomthe temperature
burn spotexperiments
area. In this werework,performed
room temperatureusing the experiments
JEOL single tilt were
stage, and high
performed temperature
using the JEOLexperiments
single tilt stage, were andperformed using theexperiments
high temperature Hummingbird were 2.3-mm heating
performed using
stage.
the TEM images were
Hummingbird analyzed
2.3-mm heatingusing ImageJ
stage. TEM[15].images were analyzed using ImageJ [15].
TheTheenergy
energy of ions
of ions produced
produced by bythetheColutron
Colutron is typically
is typically <20<20 keV,
keV, so so
thatthat
they areare
they implanted
implanted
within thetheTEM foilfoil
thickness. TheThe 2 D 2+ molecule breaks apart instantaneously upon hitting thethe
within TEM thickness. 2 D2+ molecule breaks apart instantaneously upon hitting
sample, becoming 50% of its initial energy. In the case of a 10 keV 2D ++ ion beam, 5 keV D will
sample, becoming 50% of its initial energy. In the case of a 10 keV D2 2 2 D will be
be implanted
implantedinto intothe
thesample.
sample.Ions Ions produced
produced bybythethe Tandem
Tandem accelerator
accelerator are are typically
typically in theinMeV
the MeVenergy
energy
range range
and and of much
of much higher
higher massmass (e.g.,197197
(e.g., Au)Au)andandresult
result in in high levels
levels ofofdamage
damagesimilarsimilar to to
thatthat
experienced by neutron-irradiated materials in reactors, but in a much
experienced by neutron-irradiated materials in reactors, but in a much shorter timeframe. Irradiation shorter timeframe. Irradiation
parameters
parameters were determined
were determined using Quick
using Quick Calculations
Calculations in the Monte
in the Monte Carlo-based
Carlo-based Stopping
Stopping andandRange
Range
of Ions in Matter (SRIM) code [16]. SRIM calculations are performed at an angle of 60 ◦ off surface
of Ions in Matter (SRIM) code [16]. SRIM calculations are performed at an angle of 60° off surface
normal because thethesample holder is is
tilted ◦
normal because sample holder tilted3030°toward
towardthe thebeam
beamline,line,which
whichisisnormal
normal to to the
the TEM. A
A threshold
thresholddisplacement
displacementenergy, energy,EEDD, ,of of4343eV
eVwas wasused
usedfor forAuAu[17].
[17].
AuAu TEMTEM samples
samples were wereprepared
prepared by bypulsed-laser
pulsed-laser deposition
deposition (PLD)
(PLD) depositing
depositing of 40 nm-thick
of 40 nm-thick AuAu
films
filmsonto NaCl
onto NaCl single
single crystals,
crystals, which
whichwere werecleaved
cleavedand anddissolved
dissolvedin inwater,
water,leaving
leaving the the Au
Au foil to be
be floated off onto onto aa TEM
TEM grid.
grid. TEMTEMsamples
sampleswere weresubsequently
subsequentlyannealed annealedtotoincrease
increasethe thegrain
grainsize.
size.An
An initial experiment was performed using two different ion fluxes of 2.8 MeV Au4+ . In the high flux
Materials 2017, 10, 1148 5 of 20
Materials 2017, 10, 1148 5 of 19

initial experiment
experiment, an ion beam wascurrent
performed using
of 6.2 nA two different
(9.69 × 1010 ionions/cm
fluxes of 22.8
·s)MeV
was Auused,. Inand
4+ the high flux
the sample was
experiment, an ion beam current of 6.2 nA (9.69 × 1010 ions/cm2·s) was 8used, and the 2 sample was
irradiated in situ for 38 s. In the low flux experiment, 60 pA (9.38 ×810 ions/cm · s) was used, and the
irradiated in situ for 38 s. In the low flux experiment, 60 pA (9.38 × 10 ions/cm2·s) was used, and the
samplesample
was irradiated forfor
3800 12 ions/cm2 .
× 102. The
was irradiated 3800s.s.Both sampleswere
Both samples were irradiated
irradiated to a fluence
to a fluence of123.6
of 3.6 × 10 ions/cm
The area of of
thethe
2.82.8MeV 4+ 2
area MeVAu beamspot
Au4+ beam spotwas
was estimated
estimated to10
to be bemm10 2mm . Figure
. Figure 3 shows3 shows SRIM calculations
SRIM calculations
of displacement damage
of displacement (dpa)
damage and
(dpa) andthe
theimplanted ionconcentration
implanted ion concentration forMeV
for 2.8 2.8 MeV Au4+
Au4+ into into
a Au foil.a Au foil.

Figure 3. Stopping and Range of Ions in Matter (SRIM) predicted Au concentration (at %) and damage
Figure 3. Stopping and Range4+of Ions in Matter (SRIM) predicted Au concentration (at %) and damage
dose (dpa) for 2.8 MeV Au into a Au foil for a fluence of 3.6 × 1012 ions/cm2. Filled circles indicate the
dose (dpa) for 2.8 MeV Au 4+ into a Au foil for a fluence of 3.6 × 1012 ions/cm2 . Filled circles indicate
Au concentration profile, and empty squares indicate the Au displacement damage profile. Lines of
the Aufit concentration
are only meantprofile,
to guideand empty squares indicate the Au displacement damage profile. Lines
the eye.
of fit are only meant to guide the eye.
Next, a series of samples were irradiated in situ at room temperature with various combinations
of 10akeV
Next, He,of5 samples
series keV D (resulting from a 10 keV
were irradiated in situD2 beam)
at room and 1.7 MeV Au3+with
temperature . SRIM calculations
various for
combinations of
10 keV these
He, 5beams
keV D into a Au foil from
(resulting are shown
a 10 inkeVFigure 4. Noteand
D2 beam) that,1.7
in the
MeVcaseAu of3+
He and D calculations
. SRIM implantations,for these
most of the gas will readily diffuse to the surface of the thin film. The actual implanted gas
beams into a Au foil are shown in Figure 4. Note that, in the case of He and D implantations,
concentration is expected to be significantly lower than the SRIM calculated values. Single-ion
most of the gas will
irradiations readily
include: He, Ddiffuse
and Au;to andthedouble
surface ion of the thininclude:
irradiations film. He The+ actual
D, D + Auimplanted
and gas
concentration is expected to be significantly lower than the SRIM calculated
He + Au. A final triple ion irradiation was done using all three beams simultaneously. He and He/D values. Single-ion
irradiations
beam spotinclude: He, estimated
areas were D and Au; to beand
19 mm double
2 for all ion irradiations
calculations, based include:
on multipleHe beam+ D,
spotDarea
+ Au and
measurements.
He + Au. All ion
A final triple beam
ion fluxes were
irradiation washelddonerelatively
usingconstant,
all three with He+ current
beams ranging from He and
simultaneously.
He/D 1.2 to 2.6 μAareas
(3.95 were
× 1013–8.55 × 1013 ions/cm 2·s) and the Au3+ current ranging from 5 to 20 pA
beam spot estimated to be 19 mm2 for all calculations, based on multiple beam
(1.04 × 108–4.17 × 108 ions/cm2·s, or ≈2.9 × 10−6 dpa/s) between the experiments. Higher Au currents
spot area measurements. All ion beam fluxes were held relatively constant, with He+ current
resulted in samples quickly becoming saturated with damage, making comparisons between various
rangingirradiation
from 1.2conditions
to 2.6 µA (3.95 All
difficult. 1013 –8.55
× samples were 1013 ions/cm
× irradiated 2 ·s) and the Au3+ current ranging
for at least 30 min. When calculating
from 5 fluences,
to 20 pAthe (1.04 × 108He/D × 10was
–4.172 beam 8 ions/cm2 ·s, or ≈2.9 × 10−6 dpa/s) between the experiments.
combined estimated to be 50% He and 50% D2 based on the ERD results
Higherpresented
Au currents resulted
above, in samples
where the D/He ratio quickly becoming
was determined to saturated
be 1.8, becausewith damage,the
measuring making comparisons
exact He/D 2

ratio before each experiment would be impractical. The He fluence was therefore
between various irradiation conditions difficult. All samples were irradiated for at least 30 min. taken as 50% of the
total fluence, calculated using the current recorded by the Faraday cup, and the D fluence was taken
When calculating fluences, the combined He/D2 beam was estimated to be 50% He and 50% D2
as 2 × 50% of the total fluence because the Faraday cup registers one count per D2 molecule. Specific
based on the ERD results presented above, where the D/He ratio was determined to be 1.8, because
damage dose and implanted gas concentrations are estimated within the text. Based on SRIM
measuring the exact
calculations, the He/D ratio before
Au ions2 produce about each experiment
two orders would
of magnitude bedisplacements
more impractical.than ThetheHeDfluence
and was
therefore
He taken
beams. as 50% of the
Displacement total produced
damage fluence, by calculated usinginthe
Au ions results current recorded
displacement by thetoFaraday
cascades, similar
neutron
cup, and the Dirradiation
fluence was damage, 2 × 50%
takenasasopposed to ofthethepoint
totaldefect
fluencedamage
becauseexpected to result cup
the Faraday fromregisters
implantation with low energy, low mass D and He beams. Much of the
one count per D2 molecule. Specific damage dose and implanted gas concentrations are estimated 1.7 MeV Au beam travels
through a 100 nm-thick TEM foil of most materials, while all of the He and D will implant directly
within the text. Based on SRIM calculations, the Au ions produce about two orders of magnitude
into the TEM foil, providing a mechanism for studying gas bubble formation in situ.
more displacements than the D and He beams. Displacement damage produced by Au ions results in
displacement cascades, similar to neutron irradiation damage, as opposed to the point defect damage
expected to result from implantation with low energy, low mass D and He beams. Much of the 1.7 MeV
Au beam travels through a 100 nm-thick TEM foil of most materials, while all of the He and D will
implant directly into the TEM foil, providing a mechanism for studying gas bubble formation in situ.
Materials 2017, 10, 1148 6 of 20
Materials 2017, 10, 1148 6 of 19

Figure 4. SRIM calculated (a) displacement and (b) concentration profiles as a function of depth for
Figure 4. SRIM calculated (a) displacement and (b) concentration profiles as a function of depth for Au
Au irradiated with various ion species, including 10 keV He, 5 keV D and 1.7 MeV self-ions. He and
irradiated with various ion species, including 10 keV He, 5 keV D and 1.7 MeV self-ions. He and D ion
D ion fluence of 1 × 1017 ions/cm2 and Au fluence of 1 × 1011 ions/cm2 were used in the calculations.
fluence of 1 × 1017 ions/cm
SRIM calculations
2 and Au fluence of 1 × 1011 ions/cm2 were used in the calculations. SRIM
are done at 60° off surface normal because the TEM specimen holder is tilted
calculations are ion
done ◦
at 60Theoff surface normal
toward the beam. total dpa profile (Dbecause
+ He + Au) theisTEM specimen
indicated holder
by purple is in
stars tilted toward
(a); the Au the
ion beam.
profilesThearetotal dpa by
indicated profile (D + He
red squares; He+profiles
Au) is are
indicated
indicated byby purple
yellowstars in (a);
triangles; andtheD Au profiles
profiles are are
indicated by red
indicated by squares; HeLines
blue circles. profiles
of fitare
areindicated
only meant bytoyellow triangles;
guide the eye. and D profiles are indicated by
blue circles. Lines of fit are only meant to guide the eye.
Preliminary experiments were performed on zirconium alloys and LiAlO2 with the goal of
understandingexperiments
Preliminary synergistic effects weretaking place in TPBAR
performed on zirconiummaterialsalloys
inside aandreactor.
LiAlO An2understanding
with the goal of
of defect-gas
understanding interactions
synergistic and bubble
effects takingformation
place in is of current
TPBAR interestinside
materials in thesea materials.
reactor. An Allunderstanding
zirconium
alloy TEM samples were prepared by jet polishing. In these experiments,
of defect-gas interactions and bubble formation is of current interest in these materials. All zirconium various zirconium alloys
(primarily Zircaloy-4 and optimized ZIRLO) were irradiated with combinations of 10 keV He, 5 keV
alloy TEM samples were prepared by jet polishing. In these experiments, various zirconium alloys
D and 3 MeV Zr in situ at 310 °C. In both this and the LiAlO2 experiments, elevated temperature was
(primarily Zircaloy-4 and optimized ZIRLO) were irradiated with combinations of 10 keV He, 5 keV D
used to simulate reactor conditions. Here, we present results from the He, He + D and triple ion
and 3irradiation situ at 310 ◦with
MeV Zr inexperiment C. Inall both thisions
three andsimultaneously.
the LiAlO2 experiments, elevated temperature
In these preliminary experiments,was the used
to simulate reactor conditions. Here, we present results from the He,
zirconium alloy varied, and the ion beams were left overnight in many instances, so the exact ion flux He + D and triple ion irradiation
experiment
and total with
ion all threeare
fluence ions simultaneously. In these preliminary experiments, the zirconium alloy
unknown.
varied, and AlltheLiAlOion2 samples
beams were left overnight
were prepared in many
from LiAlO instances,
2 powder drop-cast so onto
the exact
2.3-mm ionMo flux
gridsand total
with a ion
fluenceC film. LiAlO2 samples were irradiated in situ at 310 °C using various combinations of 10 keV He,
are unknown.
5 keV
All D and samples
LiAlO 1.7 MeV Au. were SRIM calculations
prepared fromwere LiAlO donepowder
using EDdrop-cast
= 10 eV foronto Li, 302.3-mm
eV for OMo andgrids
27 eV with
2 2
a C film. LiAlO2 samples were irradiated in situ at 310 C using various combinations of 10ion)
for Al [18]. In this manuscript, we present initial results from
◦ the He (single ion), He + D (double keV He,
and He + D + Au (triple ion) irradiation experiments. The 10 keV He + D2 beam was tuned in the
5 keV D and 1.7 MeV Au. SRIM calculations were done using ED = 10 eV for Li, 30 eV for O and 27 eV
morning and used for both the double and triple ion experiments, so that conditions remained as
for Al [18]. In this manuscript, we present initial results from the He (single ion), He + D (double ion)
uniform as possible. In the single ion (10 keV He) experiment, the He beam current was 4 μA (ion
and He flux+ofD1.87
+ Au × 10(triple
14 ions/cmion)2·s),irradiation
possibly lower experiments.
based on theThe burn 10spot,
keVwhich
He +indicated
D2 beamthat was thetuned
edge of in the
morningthe Heand beamused for was
profile bothhitting
the double and triple
the observable area ion
of theexperiments,
sample. The sample so that wasconditions
irradiated forremained
2 h, a as
uniformtotalasfluence
possible. In ×the
of 1.34 single
1018 ions/cm ion2. (10
Again,keVnote He)that,
experiment,
due to thethe He beam
particles beingcurrent
50–100 nm wasthick,
4 µAmost
(ion flux
of 1.87of ×
the10He14 is expected2 ·to
ions/cm s),diffuse
possibly to thelower
surfacebased
ratheronthantheimplanting
burn spot,inside which theindicated
sample, and thatthethe edge of
actual
amount remaining inside the sample should be much lower
the He beam profile was hitting the observable area of the sample. The sample was irradiated for than the SRIM predicted value. The
2 h, asample was exposed
total fluence of 1.34 to the
× 10 electron
18 ions/cmbeam 2for most ofnote
. Again, the implantation.
that, due toIn thetheparticles
double ion experiment
being 50–100 nm
(10 keV He + D2), the beam current was 3 μA (ion flux of 9.38 × 1013 ions/cm2·s). The sample was
thick, most of the He is expected to diffuse to the surface rather than implanting inside the sample,
irradiated for 2 h in situ, resulting in a total fluence of 6.75 × 1017 (He + D2)/cm2. In this experiment,
and the actual amount remaining inside the sample should be much lower than the SRIM predicted
the sample was imaged every 5 min, exposed for ≈30 s each time, plus a few minutes total for re-
value.alignment
The sample was exposed to the electron beam for most of the implantation. In the double
purposes. For the remainder of the irradiation, the electron beam was off. In the triple ion
ion experiment (10 keV Hethe
irradiation experiment, +D 2 ), the
He/D beam current was 3 µA (ion flux of 9.38 × 1013 ions/cm2 ·s).
2 beam parameters were kept exactly the same as the dual beam
The sample
experiment.was The irradiated for 2 current
Au3+ particle h in situ, was resulting
≈1.08 nAin a total
(7.18 × 1010fluence
ions/cmof 6.75
2·s) × 1017 (He
on average + Dthis
during 2 )/cm .
2

In this experiment,
experiment. The the
totalsample
irradiation wastime imaged was 2every 5 min,inexposed
h, resulting the samefor He/D≈30fluences
s eachas time, plus a few
the double
minutesbeam experiment
total and a Au fluence
for re-alignment purposes. of 5.17For×the10 remainder
14 ions/cm . The
2 combined
of the peak damage
irradiation, dose for
the electron the was
beam
off. In the triple ion irradiation experiment, the He/D2 beam parameters were kept exactly the same
as the dual beam experiment. The Au3+ particle current was ≈1.08 nA (7.18 × 1010 ions/cm2 ·s) on
average during this experiment. The total irradiation time was 2 h, resulting in the same He/D fluences
as the double beam experiment and a Au fluence of 5.17 × 1014 ions/cm2 . The combined peak damage
Materials 2017, 10, 1148 7 of 20

dose for the triple ion experiment was 42 dpa. The sample was exposed to the electron beam for the
entirety of the single and triple ion irradiation experiments.
Materials 2017, 10, 1148 7 of 19

3. Results
triple ion experiment was 42 dpa. The sample was exposed to the electron beam for the entirety of
the single and triple ion irradiation experiments.
3.1. Dose Rate Effects of In Situ Single Beam Au Irradiation into Au
Au foils nominally 40 nm in thickness were irradiated in situ with 2.8 MeV Au4+ to the same
3. Results
First,
total fluence, 3.6 × 1012 ions/cm2 , using two different fluxes of 9.38 × 108 and 9.69 × 1010 ions/cm2 ·s.
3.1. Dose Rate Effects of In Situ Single Beam Au Irradiation into Au
This equates to 0.09 displacements per atom (dpa) and peak damage dose rates of 2.5 × 10−5 and
First, Au foils nominally 40 nm in thickness were irradiated in situ with 2.8 MeV Au4+ to the
2.5 × 10−3 dpa/s. Though not ideal, samples were not aligned to a specific imaging condition
same total fluence, 3.6 × 1012 ions/cm2, using two different fluxes of 9.38 × 108 and 9.69 × 1010 ions/cm2·s.
due to the relatively small grain size. An attempt was made at maintaining a similar imaging
This equates to 0.09 displacements per atom (dpa) and peak damage dose rates of 2.5 × 10−5 and
condition 2.5 for
× 10all samples
−3 dpa/s. Though throughout all in were
not ideal, samples situ not
experiments
aligned to aby examining
specific imaging the defect
condition dueand
to grain
contrast.theFigure 5a–c
relatively shows
small grainexcerpts of thewas
size. An attempt high fluxatirradiation,
made maintaining aand Figure
similar 5e–g
imaging showsfor
condition excerpts
of the lowall flux
samples throughout
irradiation all in
at the situfluence.
same experimentsThe by examining
images the defect
in Figure 5e–g and
taken grain
from contrast.
the low flux
experimentFigure 5a–c
have shows
less excerpts damage
observable of the high fluxthe
than irradiation,
images and Figure 5a–c
in Figure 5e–g from
showstheexcerpts
high of theexperiment.
flux low
flux irradiation at the same fluence. The images in Figure 5e–g taken from the low flux experiment
The number of observed damage events per unit time was expectedly higher with a higher ion flux.
have less observable damage than the images in Figure 5a–c from the high flux experiment. The
In the high
number fluxofexperiment,
observed damage a multitude
events per of
unitdefects
time was was observed
expectedly higherafter
withonly 5 s of
a higher ionirradiation,
flux. In at
4.85 × 10the11 ions/cm2 , where only a few defects were observed in the low flux experiment. With high
high flux experiment, a multitude of defects was observed after only 5 s of irradiation, at
flux, the4.85
defect
× 1011concentration
ions/cm2, whereincreased
only a few steadily
defects were ≈30 s, until
forobserved in the defect
low fluxsaturation
experiment.seemed
With high to occur.
flux, the defect concentration increased steadily for ≈30 s, until defect saturation
A high density of irradiation-induced defects obscured most other microstructural features after seemed to occur. A
3.39 × 10 high density of
12 ions/cm 2 . irradiation-induced defects obscured
In the low flux experiment, the most
defectother microstructural
concentration features to
continued after
increase
3.39 × 1012 ions/cm2. In the low flux experiment, the defect concentration continued to increase
throughout the irradiation, reaching a defect concentration appearing to be lower than that observed
throughout the irradiation, reaching a defect concentration appearing to be lower than that observed
in the high dose
in the highrate experiment.
dose Additionally,
rate experiment. defect
Additionally, defectclusters
clustersgenerally
generally appeared
appeared totobebesmaller
smallerin in size
than those produced in the high rate experiment.
size than those produced in the high rate experiment.

Figure 5. TEM images from in situ 2.8 MeV Au4+ irradiation into a Au foil using dose rates of
Figure 5.9.69TEM 4+
× 10images
10 (a–c) andfrom9.38in ×situ
108 2.8 MeV2·sAu
ions/cm (e–g),irradiation
at fluences into a Au
of 4.85 × 10foil using
8, 1.45 × 10dose
12 andrates of
9.69 × 10 10 10 ions/cm
3.39 × (a–c)
12 2
and 9.38. (d,h)×Plots 8
10 ofions/cm 2
the number ·sof(e–g),
observable damage events
at fluences of 4.85 8
as a×function of time,
10 , 1.45 1012 and
× for
3.39 × 10the12 first 5 s of2the
ions/cm highPlots
. (d,h) flux experiment
of the numberand for
of the first 500 s damage
observable of the lowevents
flux experiment, fit with
as a function a
of time, for
linear curve indicated by the pink dashed line. The slope of the linear fit was used to determine the
the first 5 s of the high flux experiment and for the first 500 s of the low flux experiment, fit with a linear
measured flux. The entire irradiation time is not included in (d,h) because new damage events become
curve indicated by the pink dashed line. The slope of the linear fit was used to determine the measured
difficult to distinguish from existing damage once the microstructure nears damage saturation. All
flux. TheTEMentire irradiation
images were taken time is not
at the sameincluded in (d,h) because new damage events become difficult to
magnification.
distinguish from existing damage once the microstructure nears damage saturation. All TEM images
were takenFigure
at the5d,h shows
same the number of observable damage events as a function of time, during the
magnification.
first 5 s of the high flux irradiation and during the first 417 s of the low flux irradiation, taken from
the in
Figure situ shows
5d,h images.the
Note that thisof
number is observable
only a portion of each events
damage experimental time; the entire
as a function series
of time, of
during the
first 5 s of the high flux irradiation and during the first 417 s of the low flux irradiation, taken from the
in situ images. Note that this is only a portion of each experimental time; the entire series of images
Materials 2017, 10, 1148 8 of 20

was not used because once the sample accumulates enough defects, new damage events became
difficult to distinguish. New damage events became difficult to distinguish after about 5 s in the
high flux data. Thus, the plot in Figure 5d extends to 5 s, and the damage events were recorded
for about two orders of magnitude longer for the low flux data (approximately the same fluence).
The ion flux should, however, remain constant for the entire irradiation. Assuming a constant ion
flux, the slopes of the linear fits of these plots were utilized to extract a mean ion flux from the in situ
videos. Calculated ion fluxes were 1.24 × 107 and 5.5 × 109 ions/cm2 ·s for the low and high dose
rate experiments, respectively, both lower than the actual flux. This is likely a combination of (i) only
a portion of the damage events being observable in the imaging conditions show in in Figure 5 and (ii)
many ions losing energy purely due to electronic stopping as they pass through the 40 nm-thick foil.
SRIM calculations (Figure 3) indicate that most Au ions will pass directly through the Au foil during
these experiments.

3.2. In Situ Single Ion Irradiation into Au

Figure 6 shows (a–c) excerpts of the 10 keV He irradiation; (d–f) excerpts of the 1.7 MeV Au
irradiation and (g–i) excerpts of the 5 keV D irradiation. Within 20 min of irradiation with 10 keV He,
a few defects were visible, which grew into larger, more complex defect structures after 30 min. Those
structures included triangular defects, which may be stacking fault tetrahedra (SFTs). Though bubbles
were not observed in the video collected in situ due to sample motion, a still image recorded
post-irradiation using a higher resolution camera (Figure 7) indicated a homogenous distribution of
circular bubbles ≈1.5 nm in diameter. Bubbles were much more visible in grains with less defect
contrast, with an example indicated by an arrow in Figure 6. In situ irradiation with 1.7 MeV Au3+
resulted in a microstructure similar to that observed in Figure 5, with the defect concentration increasing
with time. Note that, even though the irradiation only reached 0.02 dpa after 30 min and the He
implantation reached 9.2 dpa (1.54 × 1017 ions/cm2 ) after 30 min, there is much more visible damage
in the Au irradiated sample. This illustrates the difference in resulting microstructures from cascade
(Au) vs. point defect (He) damage. No cavities were observed. In situ implantation with 5 keV D
resulted in very few microstructural changes within 30 min (1.42 × 1017 ions/cm2 , 1.8 dpa). Two defect
clusters due to D implantation are shown in Figure 6h, but disappeared and are not visible in Figure 6i.
increasing with time. Note that, even though the irradiation only reached 0.02 dpa after 30 min and
the He implantation reached 9.2 dpa (1.54 × 1017 ions/cm2) after 30 min, there is much more visible
damage in the Au irradiated sample. This illustrates the difference in resulting microstructures from
cascade (Au) vs. point defect (He) damage. No cavities were observed. In situ implantation with
5 keV D resulted in very few microstructural changes within 30 min (1.42 × 1017 ions/cm2, 1.8 dpa).
Materials 2017, 10, 1148 9 of 20
Two defect clusters due to D implantation are shown in Figure 6h, but disappeared and are not visible
in Figure 6i.

Materials 2017, 10, 1148 9 of 19

Figure 6. In situ TEM images from single beam irradiations: (a–c) 10 keV He; (d–f) 1.7 MeV Au and
Figure
(g–i) 6. InDsitu
5 keV TEM
after 10, images
20 and 30 from
min.single beam irradiations:
The arrow (a–c)toward
in (c) is pointing 10 keV aHe; (d–f)
grain 1.7 MeV
where Au and
bubbles are
(g–i) 5 keV D after 10, 20 and 30 min. The arrow in (c) is pointing toward a grain where
easily visible (shown zoomed in Figure 7). Dashed circles in (h) highlight defects that were observed bubbles are
easily
and visible
later (shown zoomed
disappeared. At 30 min,in Figure 7). Dashed
irradiation doses circles
were as infollows:
(h) highlight defects
(c) 1.54 × 1017that were2,observed
ions/cm 9.2 dpa,
and later disappeared. At 30 min, irradiation doses were as follows: (c) 1.54 × 10 17 ions/cm2 , 9.2 dpa,
31.97 at % He, (f) 7.5 × 10 ions/cm , 0.02 dpa, and (i) 1.42 × 10 ions/cm , 1.8 dpa, 30.94 at % D. All
11 2 17 2

31.97images
at % He, (f) 7.5 × 10 11 ions/cm2 , 0.02 dpa, and (i) 1.42 × 1017 ions/cm2 , 1.8 dpa, 30.94 at % D.
TEM were taken at the same magnification.
All TEM images were taken at the same magnification.
 Figure 6. In situ TEM images from single beam irradiations: (a–c) 10 keV He; (d–f) 1.7 MeV Au and
(g–i) 5 keV D after 10, 20 and 30 min. The arrow in (c) is pointing toward a grain where bubbles are
easily visible (shown zoomed in Figure 7). Dashed circles in (h) highlight defects that were observed
and later disappeared. At 30 min, irradiation doses were as follows: (c) 1.54 × 1017 ions/cm2, 9.2 dpa,
Materials at 10,
2017,
31.97 1148 (f) 7.5 × 1011 ions/cm2, 0.02 dpa, and (i) 1.42 × 1017 ions/cm2, 1.8 dpa, 30.94 at % D. All
% He, 10 of 20

TEM images were taken at the same magnification.

Figure 7. Still image taken after single ion 10 keV He implantation into Au, showing a 1.5-nm bubble
Figure 7. Stillinimage
distribution taken after
underfocus. Thissingle ion 10 keV
is a zoomed Heof
image implantation into Au, by
the grain indicated showing a 1.5-nm
an arrow bubble
in Figure 6c.
distribution in underfocus. This is a zoomed image of the grain indicated by an arrow in Figure 6c.
A few bubbles are indicated by arrows.
A few bubbles are indicated by arrows.
3.3. In Situ Double Ion Irradiation into Au
3.3. In Situ Double Ion Irradiation into Au
Figure 8 shows (a–c) excerpts from the He + D irradiation; (d–f) excerpts from the D + Au
Figure
irradiation and 8 shows (a–c) excerpts
(g–i) excerpts from thefrom
He +theAuHe + D irradiation;
irradiation. In these (d–f) excerptsthe
experiments, from
ionthe D +were
fluxes Au
irradiation and (g–i) excerpts from the He + Au irradiation. In these experiments, the ion
kept approximately equal to the single ion experiments just described. Dual ion He + D irradiation fluxes were
kept approximately
resulted in very few equal to the single
microstructural ion experiments
changes justSome
after 30 min. described. Dual ion
small defects He observed
were + D irradiation
at the
resulted in very few microstructural changes after 30 min. Some small defects were observed
end of the irradiation in Figure 8c. Dual ion D + Au irradiation resulted in defect and cavity at the end
of the irradiation in Figure 8c. Dual ion D + Au irradiation resulted in defect and cavity
production. Through-focus imaging [19] was found difficult, especially in situ, due to sample motionproduction.
Through-focus imaging [19] was found difficult, especially in situ, due to sample motion and the
high levels of defect contrast, but some defects appear to be cavities. It is important to note that
distinguishing between large cavities and craters has been proven difficult in Au [20,21]. Cavity-like
structures were measured to be 8–12 nm in diameter in Figure 8e and grew as the irradiation continued,
measuring at 10–15 nm in diameter in Figure 8f. Cavity size and density differed significantly from
those produced by He alone. There was significantly more cavity formation in the Au + D case than in
the pure Au or pure D case.
and the high levels of defect contrast, but some defects appear to be cavities. It is important to note
that distinguishing between large cavities and craters has been proven difficult in Au [20,21]. Cavity-like
structures were measured to be 8–12 nm in diameter in Figure 8e and grew as the irradiation
continued, measuring at 10–15 nm in diameter in Figure 8f. Cavity size and density differed
Materials 2017, 10,from
significantly 1148 those produced by He alone. There was significantly more cavity formation11inofthe
20

Au + D case than in the pure Au or pure D case.

Figure 8. In situ TEM images from double beam irradiations: (a–c) 10 keV He + 5 keV D; (d–f) 1.7 MeV
Figure
Au + 58.keV In situ TEM(g–i)
D and images from double
1.7 MeV Au + 10beam
keV irradiations:
He after 10, (a–c) 10 keV
20 and He +Dashed
30 min. 5 keV D; (d–f) highlight
circles 1.7 MeV
Au + 5 keV D and (g–i) 1.7 MeV Au + 10 keV He after 10, 20 and 30 min. Dashed
possible cavity formation. At 30 min, irradiation doses were as follows: (c) 8.88 × 10 D/cm2 and circles
16 highlight
possible × 10 16 2
4.44 × 10cavity
16 He/cmformation.
2, 1.1 D dpa At and
30 min, irradiation
2.7 He doses
dpa, 19.35 at %were
D andas9.22
follows: (c) 8.88
at % He, (f) 1.42 × 10D/cm
17 D/cm2and and
16 2 17 2
1.88×× 10
4.44 He/cm2, 1.8
1011 Au/cm , 1.1DDdpadpaandand0.005
2.7 He
Audpa,
dpa,19.35
30.94atat%%DD,and 9.22
and (i) at % ×He,
1.54 1.42 ×
1017(f)He/cm 10 7.5
2 and D/cm× 1011
and
Au/cm 1011
1.882, ×9.2 HeAu/cm
dpa and
2 , 1.8 D dpa and 0.005 Au dpa, 30.94 at % D, and (i) 1.54 × 1017 He/cm2 and
0.02 Au dpa, 31.97 at % He. All TEM images were taken at the same
11 2
7.5 × 10 Au/cm , 9.2 He dpa and 0.02 Au dpa, 31.97 at % He. All TEM images were taken at the
magnification.
same magnification.
Dual ion He + Au irradiation resulted in defects and large cavity-like features. Defect and
apparent ion
Dual He +concentration
cavity Au irradiationappeared
resulted in
todefects
increaseandwith
largedamage
cavity-like features.
dose and HeDefect and apparent
concentration. The
cavity concentration
cavity-like appeared by
features, indicated to increase with
red circles, damage
ranged dose
in size and7–20
from He concentration.
nm throughoutThe thecavity-like
irradiation
features, indicated
and tended by red
to exhibit circles,
oblong ranged
shapes. in size
These from 7–20
features againnm throughout
differed from the irradiation
those observedand tended
during the
to exhibit oblong shapes. These features again differed from those observed during the
single beam He implantation, where bubbles were consistently smaller and round. Rapid nucleationsingle beam He
implantation, where bubbles were consistently smaller and round. Rapid nucleation of cavities was
captured in a few instances during multiple ion irradiation. Figure 9a–d shows cavity nucleation during
the Au + D irradiation, with the initial microstructure in Figure 9a and the final cavity appearance
in Figure 9d. The cavity is first apparent in Figure 9b, although it appears faint, as it nucleated during
Materials 2017, 10, 1148 11 of 19

of cavities
Materials was
2017, captured in a few instances during multiple ion irradiation. Figure 9a–d shows cavity
10, 1148 12 of 20
nucleation during the Au + D irradiation, with the initial microstructure in Figure 9a and the final
cavity appearance in Figure 9d. The cavity is first apparent in Figure 9b, although it appears faint, as
the acquisition of this video frame. Given the frame rate of 15 FPS, a maximum nucleation time of
it nucleated during the acquisition of this video frame. Given the frame rate of 15 FPS, a maximum
111 ms can be established. The cavity appears more clearly in Figure 9c and may have expanded
nucleation time of 111 ms can be established. The cavity appears more clearly in Figure 9c and may
slightly before the stable structure in (d) was reached.
have expanded slightly before the stable structure in (d) was reached.

Figure 9. In situ TEM images showing cavity growth as a function of time due to (a–d) double ion
Figure 9. In situ TEM images showing cavity growth as a function of time due to (a–d) double ion
irradiation with 5 keV D + 1.7 MeV Au and cavity formation and collapse as a function of time due to
irradiation with 5 keV D + 1.7 MeV Au and cavity formation and collapse as a function of time due
(e–h) triple ion irradiation with 10 keV He, 5 keV D and 2.8 MeV Au. Dashed circles highlight the
to (e–h) triple ion irradiation with 10 keV He, 5 keV D and 2.8 MeV Au. Dashed circles highlight the
cavity of interest in each image. Approximate fluences in (e–h) were Au: 1.2 × 101313, He: 1.3 × 1015
15 and
cavity of interest in each image. Approximate fluences in (e–h) were Au: 1.2 × 10 , He: 1.3 × 10 and
D: 2.2 × 101515ions/cm2. 2TEM images (a–d) were taken at the same magnification (scale bar in (a)), and
D: 2.2 × 10 ions/cm . TEM images (a–d) were taken at the same magnification (scale bar in (a)), and
(e–h) were taken at the same magnification (scale bar in (e)).
(e–h) were taken at the same magnification (scale bar in (e)).

3.4. In Situ Triple Ion Irradiation into Au

3.4. In Situ Triple Ion Irradiation into Au
Figure 10 shows the microstructural progression of Au under triple ion irradiation. Triple ion
Figure 10 shows the microstructural progression of Au under triple ion irradiation. Triple ion
irradiation resulted in a steady increase in the concentration of defect clusters. An increasing number
irradiation resulted in a steady increase in the concentration of defect clusters. An increasing
of structures thought to be large cavities gradually appeared during the irradiation, with one possible
number of structures thought to be large cavities gradually appeared during the irradiation, with
cavity at 20 min (Figure 10b), having a measured diameter of 19 nm. After 30 min of irradiation
one possible cavity at 20 min (Figure 10b), having a measured diameter of 19 nm. After 30 min
(Figure 10c), more possible cavities are apparent, which had measured diameters of 19–20 nm.
of irradiation (Figure 10c), more possible cavities are apparent, which had measured diameters of
Cavities are spread heterogeneously throughout the sample. Some cavities were observed to rapidly
19–20 nm. Cavities are spread heterogeneously throughout the sample. Some cavities were observed
appear in a process similar to what was presented in Figure 9a–d. One instance is illustrated in
to rapidly appear in a process similar to what was presented in Figure 9a–d. One instance is illustrated
Figure 9e–h, where a cavity both nucleated and collapsed quickly during a separate triple ion
in Figure 9e–h, where a cavity both nucleated and collapsed quickly during a separate triple ion
irradiation experiment using 2.8 MeV Au, 10 keV He and 5 keV D. The microstructure prior to cavity
irradiation experiment using 2.8 MeV Au, 10 keV He and 5 keV D. The microstructure prior to cavity
nucleation is shown in Figure 9e. Within a few frames, the fully-grown cavity is shown in Figure 9f.
nucleation is shown in Figure 9e. Within a few frames, the fully-grown cavity is shown in Figure 9f.
Defect clusters caused by incoming ions appeared in the vicinity of the cavity, and the cavity began
Defect clusters caused by incoming ions appeared in the vicinity of the cavity, and the cavity began to
to disappear in Figure 9g. After a few seconds, the cavity is no longer visible in Figure 9h.
disappear in Figure 9g. After a few seconds, the cavity is no longer visible in Figure 9h.
Materials 2017, 10, 1148 13 of 20
Materials 2017, 10, 1148 12 of 19

Figure 10. In situ TEM images from triple ion beam irradiation with 10 keV He, 5 keV D and 1.7 MeV
Figure
Au In situ
10. after
shown (a)TEM images
10 min, from
(b) 20 mintriple
and ion beam
(c) 30 min.irradiation with 10
Dashed circles keV He,
indicate 5 keV Dcavity
possible and 1.7 MeV Au
formation.
At 30 min, irradiation doses were as follows: 7.11 × 10 D/cm + 3.55 × 10 He/cm + 1.88 × 10 Au/cmAt
shown after (a) 10 min, (b) 20 min and (c) 30 min. Dashed
16 circles
2 indicate16possible
2 cavity formation.
11 2,

30 min, irradiation doses were as follows: 7.11 × 1016 D/cm2 + 3.55 × 1016 He/cm2 + 1.88 × 1011 Au/cm2 ,
2.1 He + 0.88 D + 0.005 Au dpa and 7.37 at % He + 15.49 at % D. All TEM images were taken at the
2.1 Hemagnification.
same + 0.88 D + 0.005 Au dpa and 7.37 at % He + 15.49 at % D. All TEM images were taken at the
same magnification.
3.5. In Situ Single, Double and Triple Ion Irradiation in TPBAR Materials
3.5. In Situ Single, Double and Triple Ion Irradiation in TPBAR Materials
Tritium-producing burnable absorber rods (TPBARs) consist of a lithium aluminate (LiAlO2)
pelletTritium-producing
that is surrounded burnable by inner and absorber rods (TPBARs)
outer layers consist
of Zircaloy-4. The of a lithium
rods aluminate
are designed (LiAlO2 )
for placement
pellet that
inside is surrounded
a nuclear by inner and
reactor, currently the outer layers Bar
TVA Watts of Zircaloy-4.
reactor. The The rodslayer
outer are designed
acts as a for placement
getter for 3H,
inside a nuclear reactor, currently the TVA Watts Bar reactor. The
and the inner layer acts to reduce tritium oxide ( H2O) emerging from the pellet so that H can
3 outer layer acts as a getter
3 for 3be
H,
and the inner layer acts to reduce tritium oxide ( 3 H O) emerging from the pellet so that 3 H can be
gettered. The LiAlO2 pellet is enriched with the 6Li isotope, 2 which absorbs neutrons from the reactor,
gettered. The LiAlO pellet is enriched with the 6 Li isotope, which absorbs neutrons from the reactor,
becoming Li, which fissions to H + He in less than 1 s. Tritium will eventually β-decay to 3He with
7 2 3 4
7 to 3are 4 He in less than 1 s. Tritium will eventually β-decay to 3 He
abecoming
half-life ofLi, which
12.3 years.fissions
TPBARs H +surrounded by reactor-grade stainless steel cladding with an
with a half-life
aluminide coatingof 12.3 years. TPBARs
to prevent are surrounded
inward diffusion of hydrogen by reactor-grade
from the coolantstainless
andsteel cladding
outward with
diffusion
an aluminide coating to prevent inward diffusion of hydrogen from
of tritium [22]. Predicting the longevity of the TPBAR relies on a thorough understanding of the coolant and outward diffusion
of tritium [22].
gas-defect Predicting
interactions the longevity
inside both the LiAlOof the2TPBAR
pellet and relies
theon a thorough
Zircaloy-4 at understanding of gas-defect
elevated temperatures. The
interactions
damage doseinside bothinside
of pellets the LiAlO 2 pellet
the Watts Barand the Zircaloy-4
reactor is expected atto
elevated temperatures.
be approximately The damage
20 dpa.
doseFigure
of pellets11ainside
showsthe theWatts
initialBar reactor is expected
microstructure to be approximately
of zirconium alloy (ZIRLO 20 anddpa.
Zircaloy-4) samples.
Figure 11a shows the initial microstructure of zirconium
Black, circular regions shown in Figure 11a are possibly precipitates. Zirconium alloy (ZIRLO and Zircaloy-4)
alloyssamples.
were
Black, circular regions shown in Figure 11a are possibly precipitates.
irradiated at 310 °C with various combinations of 10 keV He, 5 keV D and 3 MeV Zr. A high defect Zirconium alloys were irradiated
at 310 ◦ C
density with
was various by
produced combinations of 10 keV He,
10 keV He irradiation 5 keV11b),
(Figure D andbut3no MeV Zr. Aformation
bubble high defect density
was observed.was
produced
Dual ion He by+10ZrkeV He irradiation
irradiation (Figure(Figure 11b), but
11c) resulted in ano bubble
higher formation
density was observed.
of defects Dual ion
than the single ion
He + Zr irradiation (Figure 11c) resulted in a higher density of defects than
irradiation, and triple ion irradiation (Figure 11d) resulted in a microstructure completely saturated the single ion irradiation,
and triple
with ionThe
defects. irradiation
high levels(Figure 11d) resulted
of defect contrast in in athemicrostructure completely
double and triple saturated made
ion irradiations with defects.
cavity
The high levels
observation andofdefect
defectanalysis
contrastdifficult.
in the double and triple
No cavities wereionobserved
irradiations made
in any cavity
of the observation
irradiated and
samples
defect analysis difficult. No cavities were observed in any of the irradiated
during the in situ experiments. Samples were stored for 30 days at room temperature in vacuum after samples during the in situ
experiments. Samples were stored for 30 days at room temperature
the experiment, then characterized. After 30 days, a high density of homogenously-distributed in vacuum after the experiment,
then characterized.
circular cavities wasAfter 30 days,
observed in aall
highHedensity
implanted of homogenously-distributed
samples, an example of circular which is cavities
shownwas in
observed
Figure 11e–f. in all He implanted samples, an example of which is shown in Figure 11e–f.
Materials 2017, 10, 1148 14 of 20

Materials 2017, 10, 1148 13 of 19

Figure 11. Pristine zirconium alloy structure is shown in (a). In situ TEM images from triple ion beam
Figure 11. Pristine zirconium alloy structure is shown in (a). In situ TEM images from triple ion beam
irradiation of various zirconium alloys with (b) 10 keV He, (c) 10 keV He + 3 MeV Zr and (d) 10 keV
irradiation of various zirconium alloys with (b) 10 keV He, (c) 10 keV He + 3 MeV Zr and (d) 10 keV
He + 5 keV D + 3 MeV Zr. Cavities observed 30 days after irradiation are shown in (e) underfocus
He + 5 keV D + 3 MeV Zr. Cavities observed 30 days after irradiation are shown in (e) underfocus and
and (f) overfocus.
(f) overfocus.

Initial and final states of LiAlO2 powders irradiated in situ at 310 °C for 120 min are shown in
Initial and final states ofwill
LiAlO ◦ C for 120 min are shown in
Figure 12. LiAlO 2 powders form 2 powders
small voids irradiated
due to in 200situ
keVat 310
electron beam irradiation alone,
Figure
likely due12. LiAlO 2 powders will
to displacement of Liform
or Osmall
atomsvoids
by thedueelectron
to 200 keV electron
beam. The beam
electron irradiation alone, likely
beam-induced void
due to displacement of Li or O atoms by the electron beam. The electron beam-induced
production rate varies depending on the particle, resulting in very complicated in situ void analysis. void production
rate
Voids varies
havedepending
been observed on the particle,
to form dueresulting in very
to the electron beamcomplicated
alone after inas
situ void
little analysis.
as 1–2 min ofVoids have
exposure.
been observed
All cavities in to form due
Figure to the electron
12 where confirmed beamby alone after as little
through-focal as 1–2 In
imaging. mintheof exposure.
single andAll cavities
triple ion
in Figure 12 where confirmed by through-focal imaging. In the single
irradiation experiments, the electron beam was left on, while in the dual ion experiment, the electron and triple ion irradiation
experiments,
beam was leftthe off,electron beam
except for was left
imaging andon,alignments.
while in theIndual ion experiment,
the single the electronexperiment
ion He implantation beam was
left off, except for imaging and alignments. In the single ion He implantation
(Figure 12d,g), several cavities were observed at the edges of the particle. After the double experiment (Figure 12d,g),
ion
several cavities were observed at the edges of the particle. After the double
experiment, He + D (Figure 12e,h), small bubbles were observed at the edges of the particle (thinnest ion experiment, He +D
(Figure
regions 12e,h),
with less small bubblesafter
contrast) wereanobserved
hour of at the edges Due
irradiation. of thetoparticle
contrast (thinnest
changesregions with less
throughout the
contrast) after an hour of irradiation. Due to contrast changes throughout
irradiation, the exact time of initial bubble formation was not easily determined, but estimated to be the irradiation, the exact
time
after of initial bubble
a fluence of 1.5 ×formation
1017 ions/cm was2 (≈16
not easily
at %) determined, but estimated
under He implantation to be
alone andafter a fluence
under of
dual ion
17 2
(He×
1.5 10 after
+ D) 1.7 × 1017(≈
ions/cm 16 at 2%)
He/cm (≈19under
at %) He
andimplantation
3.4 × 1017 D/cm alone
2 (≈20and
at %).under dual ion that
This suggests (He He+ D) after
content
1.7 × 10 17 He/cm2 (≈19 at %) and 3.4 × 1017 D/cm2 (≈20 at %). This 2suggests that He content may
may be the dominating factor in bubble nucleation, independent of the H content inside the material.
be thethat
dominating factor in bubble nucleation, are independent 2 H content inside the material.
of the calculated
Note the gas concentrations in parentheses the peak values by SRIM and are not
Note that the gas
representative concentrations
of the in parentheses
actual gas concentration are the peak
remaining values
inside calculated
the sample, by SRIM
which and are due
is unknown not
representative of the actual gas concentration remaining
to an unknown rate of outward diffusion of He and D to surfaces. inside the sample, which is unknown due to
an unknown rate of outward diffusion of He and D to surfaces.
Materials 2017, 10, 1148 15 of 20

Materials 2017, 10, 1148 14 of 19

Figure 12. TEM images from before and after single, double and triple ion irradiation at 310 °C in
Figure 12. TEM images from before and after single, double and triple ion irradiation at 310 ◦ C
LiAlO2. (a–c) The particles before irradiation; (d–f) The particles in underfocus after irradiation and
in LiAlO . (a–c) The particles before irradiation; (d–f) The particles in underfocus after irradiation
(g–i) the 2particles in overfocus after irradiation with 10 keV He, 10 keV He + 5 keV D and
and (g–i) the particles in overfocus after irradiation with 10 keV He, 10 keV He + 5 keV D and
10 keV He + 5 keV D + 1.7 MeV Au, respectively. (a,c,d,f) were taken at −518-nm defocus, and (b,e)
10 keV He + 5 keV D + 1.7 MeV Au, respectively. (a,c,d,f) were taken at −518-nm defocus, and (b,e)
were taken at −1-μm defocus. (g,i) were taken at +518-nm defocus, and (h) was taken at +1-μm
were taken at −1-µm defocus. (g,i) were taken at +518-nm defocus, and (h) was taken at +1-µm defocus.
defocus. The electron beam was on during the single and triple ion irradiations, but off during the
The electron beam was on during the single and triple ion irradiations, but off during the majority of
majority of the double ion irradiation. The dashed circle in (e) indicates the region where cavities are
the double ion irradiation. The dashed circle in (e) indicates the region where cavities are most visible.
most visible. All TEM images were taken at the same magnification.
All TEM images were taken at the same magnification.

The
The particle
particle utilized
utilized for
for triple
triple ion
ion irradiation
irradiation (Figure
(Figure 12c)
12c) did
did contain
contain some
some pre-existing
pre-existing voids,
voids,
but most of the particle was void-free. Triple ion irradiation resulted
but most of the particle was void-free. Triple ion irradiation resulted in an entirely different in an entirely different
microstructure
microstructure (Figure
(Figure12f,i)
12f,i)than
thandouble
double and
andsingle
singleionion
irradiation.
irradiation.Though
Thoughexamination
examinationof theoffinal
the
state images indicates a drastic change in the microstructure, the mechanism
final state images indicates a drastic change in the microstructure, the mechanism for this change for this change cannot
be elucidated
cannot with finalwith
be elucidated images
finalalone.
imagesA closer
alone.look at select
A closer lookin situ images
at select in is provided
situ imagesinisFigure
provided13.
Figure 13a shows a region with very few pre-existing voids. After just 5
in Figure 13. Figure 13a shows a region with very few pre-existing voids. After just 5 min ofmin of triple ion irradiation,
Figure 13birradiation,
triple ion shows a significant
Figure 13b increase
shows inathe cavity density.
significant increaseSome possible
in the cavitycavities
density. areSome
circled in the
possible
image.
cavitiesIncreasing
are circled the irradiation
in the time appears
image. Increasing to increasetime
the irradiation theappears
void size, as shown
to increase theatvoid
25 min
size, in
as
Figure 13c, after 60 min in Figure 13d and after 90 min in Figure 13e. The
shown at 25 min in Figure 13c, after 60 min in Figure 13d and after 90 min in Figure 13e. The final final microstructure
(Figure 13f) appears
microstructure to contain
(Figure 13f) appearslarge to
blisters thatlarge
contain possibly caused
blisters that cracking
possibly of the material.
caused crackingDrastic
of the
changes
material. Drastic changes in the crack microstructure, indicated after 5 min by an arrow incan
in the crack microstructure, indicated after 5 min by an arrow in Figure 13b, also13b,
Figure be
observed throughout the in situ irradiation. The final microstructure could not
can also be observed throughout the in situ irradiation. The final microstructure could not be focusedbe focused to a single
eucentric point inside the microscope, indicating a significant increase in topology. Some of this
to a single eucentric point inside the microscope, indicating a significant increase in topology. Some of
microstructural change is likely due to synergy between ion irradiation and the electron beam, so
other particles were imaged after the irradiation. Large, platelet-like cavities were observed in other
Materials 2017, 10, 1148 16 of 20

this microstructural change is likely due to synergy between ion irradiation and the electron beam, so
other particles
Materials were
2017, 10, 1148 imaged after the irradiation. Large, platelet-like cavities were observed15 inofother
19
particles, with less blistering and cracking of the microstructure. It is difficult to distinguish between
particles,
areas that werewithexposed
less blistering
to theand cracking
electron beamof the
andmicrostructure.
areas that wereItnot
is difficult
exposed, to distinguish
however. between
areas that were exposed to the electron beam and areas that were not exposed, however.

Figure 13. In situ TEM images showing microstructural evolution of LiAlO2 under triple ion
Figure 13. In with
irradiation situ TEM imagesbeam
the electron showing microstructural
on the sample. (a) Theevolution of LiAlO2 under
initial microstructure triplevoid-free,
appears ion irradiation
but
with the electron beam on the sample. (a) The initial microstructure appears void-free, but
(b) cavity-like structures appear after 5 min and continue to grow in (c,d) until large blisters (b) cavity-like
appear
structures appear
to crack the after 5 mininand
microstructure (e,f).continue to grow
Dashed circles in (c,d)
indicate until large
a region blisters
containing appear to crack
easily-visible defectsthe
microstructure in (e,f). Dashed circles indicate a region containing easily-visible
believed to be cavities. All TEM images were taken at the same magnification. defects believed to be
cavities. All TEM images were taken at the same magnification.
4. Discussion
4. Discussion
The He + D beam emitted from the Colutron is an interesting study in ion accelerator physics. A
fullThe
characterization
He + D beamofemitted this source
fromis the
beyond the scope
Colutron is anofinteresting
this paper; however,
study in ionit has been notedphysics.
accelerator that
the beam
A full current varies
characterization withsource
of this the partial pressures
is beyond of the of
the scope two source
this paper;gasses in a manner
however, that does
it has been noted not
that
appear to be completely linear. Experiments in this work utilized the same
the beam current varies with the partial pressures of the two source gasses in a manner that does not accelerator settings for
consistency.
appear As stated earlier,
to be completely linear.the ERD experiments
Experiments in thisconsistently
work utilizedrevealed fluences
the same approximately
accelerator onefor
settings
order of magnitude lower than those estimated by the Faraday cup current
consistency. As stated earlier, the ERD experiments consistently revealed fluences approximately one and also consistently
found a D to He ratio of approximately 1.8. Lower measured He and D concentration is probably due
order of magnitude lower than those estimated by the Faraday cup current and also consistently found
to some gas diffusing to and escaping at the surface between the time of implantation and the time
a D to He ratio of approximately 1.8. Lower measured He and D concentration is probably due to some
of the ERD measurement. Fluences calculated using the Faraday cup current should be of reasonable
gas diffusing to and escaping at the surface between the time of implantation and the time of the ERD
accuracy and have thus been used throughout the paper for the reported fluences of different
measurement. Fluences calculated using the Faraday cup current should be of reasonable accuracy
ion species.
and have thus been used throughout the paper for the reported fluences of different ion species.
Systematic experiments on Au, a model face-centered cubic (FCC) crystal structure, were
Systematic
utilized to gainexperiments on Au, a model
a basic understanding of theface-centered cubic (FCC)
type of synergistic effectscrystal structure,
one might were utilized
see during an in
to situ
gaintriple
a basic understanding of the type of synergistic effects one might
ion irradiation experiment, compared to in situ single and double ion irradiation.see during an in situThe
triple
ionresults
irradiation experiment,
here suggest that ioncompared to insome
flux may have situ single and
effect on thedouble ion irradiation.
final structure The results
of the defects. here
It should
suggest thatthat
be noted ionthe
fluxgrains
may havein thesome effect
low and on flux
high the final
casesstructure
presentedofherethe defects.
were notItoriented
should be noted that
identically
thewith
grains in thetolow
respect theand high flux
electron cases
beam, sopresented here were
a quantitative not oriented
comparison identically with
is unwarranted. respect
However, a to
thequalitative
electron beam,reasonsofor
a quantitative
this observationcomparison is unwarranted.
is that defect However,
clusters produced a qualitative
by MeV-range Aureason
ions infor
Authis
often evolve over seconds or minutes. In the low flux experiment, defect clusters often remained
undisturbed for seconds to tens of seconds (if not longer) before interacting with another cascade
Materials 2017, 10, 1148 17 of 20

observation is that defect clusters produced by MeV-range Au ions in Au often evolve over seconds
or minutes. In the low flux experiment, defect clusters often remained undisturbed for seconds to
tens of seconds (if not longer) before interacting with another cascade produced by the next incoming
ion. The case was quite different with the high flux case, where cascades rapidly occurred one after
another. The effects of flux in in situ ion irradiation TEM experiments remain an intriguing, but
incompletely explored area. Dose rate effects of heavy ion irradiation were first explored to help refine
the experimental parameters for triple ion irradiation experiments. In situ ion irradiation allows for
observation of individual damage events and quantification of damage formation as a function of
time. In a larger grained material, the two samples could be oriented to the same diffraction condition
to quantify the changes in defect density, and therefore defect recovery properties, as a function of
ion flux.
In situ single ion irradiations illustrated the most fundamental defects one would expect to occur
due to the individual ions, with the same ion flux and fluence, without any synergistic effects. Due to
the lower mass and energy of He and D in these irradiations, only small black spots resulting from
point defect production were observed. In comparison, the heavy ion, higher energy Au irradiation
produced displacement cascades that resulted in a visibly more complex defect structure, even though
the Au ion flux was three orders of magnitude lower than the He and D flux. Of all single ion irradiation
experiments, cavities were only observed in the case of He ion irradiation. Combining ion beams
with in situ double ion irradiation resulted in different microstructures. In the sample implanted with
He + D, no bubble formation occurred, only small black spot formation, after 30 min. This, combined
with the lack of bubble formation in single ion D-irradiated Au, indicates that bubble nucleation may
be dominated by He in Au; after 30 min, the He concentration in the He + D experiment was estimated
to be half of that achieved during the single ion irradiation experiment. If bubble nucleation were
equally influenced by both gas species, bubbles should be observed at the same fluence in both He and
He + D irradiations. Though no cavities were observed in samples irradiated with the Au beam alone,
dual ion irradiation with D + Au and He + Au, to approximately the same Au fluence, resulted in cavity
formation in both samples. This result compliments the results of Chisholm et al., where successive Au
irradiation followed by He implantation and He implantation followed by Au irradiation resulted in
no cavity formation, but in situ dual beam irradiation with He + Au did result in cavity formation [23],
suggesting a propensity for cavity formation in Au under dual ion irradiation. During multi-ion
irradiation, gas atoms may act to stabilize voids produced by displacement cascades, eventually
resulting in visible cavities. Cavities did seem to form more readily in samples irradiated He + Au
and D + Au than in samples irradiated with He + D. Cavity-like structures were observed after 10 min
in the sample irradiated with He + Au, a much lower He concentration than the sample irradiated
with He + D, where cavities were not observed, after 30 min of irradiation. This could be due to the
expected decrease in He mobility as the microstructure evolves [24]. Significantly more microstructural
evolution occurs during Au irradiation than during implantation with He, D, or both simultaneously.
In addition, larger vacancy clusters may form due to cascade damage than the point defect damage
produced by He or D irradiation, creating additional trapping sites for He atoms, allowing them to
more readily nucleate cavities. Nevertheless, the combination of displacement cascade damage and gas
accumulation seems to create a more favorable environment for cavity formation than gas implantation
alone. These cascade-gas interactions seem to be the dominant synergistic effect in Au, as evidenced
by the significant difference in cavity growth between single and dual ion irradiations and the lack of
a significant difference between dual and triple ion irradiations. Cavity formation and disappearance,
shown in Figure 9, were observed in a few instances during both double ion D + Au irradiation, as well
as during triple ion irradiation. Displacement cascade damage has been shown to influence He bubbles
in materials. Donnelly et al. [25] saw athermal migration, coalescence and disintegration of He bubbles
in Au under 400 keV Ar ion irradiation at 227 ◦ C. They formed underpressurized bubbles in Au by He
ion irradiation and subsequent annealing, but Ar irradiation caused the bubbles to reach equilibrium
pressure after only 0.6 dpa. Bubble disappearance is thought to be due to either bubble migration to the
Materials 2017, 10, 1148 18 of 20

surface, followed by crater formation and surface reconstruction, or by a single cascade event resulting
in He re-solution. Cascade-induced He re-solution has also been hypothesized by Ghoniem [24].
In zirconium alloys, single ion He implantation, double ion He + Zr irradiation and triple ion
irradiation with He, D and Zr at 310 ◦ C resulted in similar microstructures. These samples seemed
to form defects that were much more difficult to study, presumably due to the complex chemistry
and propensity for hydride formation in ZIRLO and Zircaloy. No bubbles were observed in situ,
even after irradiating at 310 ◦ C overnight, but cavities were observed in the same samples 30 days
post-irradiation. The reasoning for bubble formation post-irradiation is not well understood, as He
should be mobile at room temperature in zirconium [26]. Speculating, this behavior could be due
to electron beam effects or complex He-V or He-D-V cluster diffusion processes may be leading to
bubble formation on a longer timescale. In LiAlO2 samples irradiated in situ at 310 ◦ C with He,
He + D and He + D + Au irradiation resulted in significantly different microstructures. In this material,
deconvoluting electron beam effects is difficult, as the electron beam has been observed to produce
small voids at different rates in different particles. Additionally, many particles have a pre-existing
nano-sized void concentration. Interestingly, the He concentration required for bubble formation in
the single and double ion irradiation experiments was similar, indicating that He dominates bubble
formation in this material and that the D concentration does not have an effect on He bubble nucleation.
Similar behavior was observed in the Au ion irradiation experiments. Triple ion irradiation resulted
in a significantly different microstructure than single and dual ion irradiation. Single and dual ion
irradiation experiments resulted in a low density of nanometer-scale bubbles. Examination of in
situ images from the triple ion irradiation experiment elucidated some of the irradiation damage
process. Though the sample did contain some pre-existing voids, several regions within the observable
area were free of voids. Cavity-like structures appeared after 5 m and seemed to grow into larger,
platelet-like structures with time. By the end of the 2-h irradiation, all structures previously believed
to be cavities had evolved into large, platelet-like structures, possibly blisters, which appeared to crack
and break apart the microstructure.

5. Conclusions
This novel technique of in situ triple ion beam irradiation provides an excellent method for
deconvoluting reactor and other complex irradiation environments. When done sequentially with
single and double ion irradiation, these experiments elucidate kinetic processes previously difficult
to understand through experimental efforts. While real-time observation of defect evolution due
to ion irradiation is only available through this technique, electron beam effects, such as electron
beam-induced void formation, and thin film effects, such as defect and gas migration to free
surfaces, influence the microstructural evolution and must be considered. This initial work illustrates
the type of synergistic interactions observable by combining different irradiation conditions and
provides a foundation for understanding the fundamental interactions of defects in different materials
and environments.

Acknowledgments: The authors thank Clark Snow, Patrick Price, Mark Kirk, Jonathan A. Hinks and Aurilie
Gentlis for helpful discussions. The Au work was supported by the U.S. Department of Energy, Office of Science,
Materials Sciences and Engineering Division, under FWP Award #15013170. The Zr work was supported by the U.S.
Department of Energy’s Nuclear Energy University Program (DE-NE0000678). The work on TPBAR materials was
supported by the NNSA Tritium Sustainment Program. Sandia National Laboratories is a multi-mission laboratory
managed and operated by the National Technology and Engineering Solutions of Sandia, LLC, a wholly-owned
subsidiary of Honeywell International, Inc., for the U.S. Department of Energy’s National Nuclear Security
Administration under contract DE-NA0003525.
Author Contributions: C.A.T. analyzed the data, did the SRIM calculations, created the figures, performed the
LiAlO2 experiments and prepared the manuscript. D.C.B. performed the Au experiments, and B.R.M. performed
the zirconium alloy experiments. D.S. provided LiAlO2 samples and technical input. D.C.B. and B.D. performed
the ERD experiments. M.S. and B.D. designed the accelerator beam line electromagnet and steering system. J.D.
created SolidWorks drawings of the facility. D.B. and K.M.H. designed and built the facility. K.M.H. led the
experimental work.
Materials 2017, 10, 1148 19 of 20

Conflicts of Interest: The authors declare no conflict of interest. The funding sponsors had no role in the design of
the study; in the collection, analyses or interpretation of data; in the writing of the manuscript; nor in the decision
to publish the results.

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