metals

Article
Effect of Heavy Ion Irradiation Dosage on the
Hardness of SA508-IV Reactor Pressure Vessel Steel
Xue Bai 1,2,3, *, Sujun Wu 1,3, *, Peter K. Liaw 2 , Lin Shao 4 and Jonathan Gigax 4
1 School of Materials Science and Engineering, Beihang University, Beijing 100191, China
2 Department of Materials Science and Engineering, The University of Tennessee, Knoxville,
TN 37996, USA; pliaw@utk.edu
3 Beijing Key Laboratory of Advanced Nuclear Materials and Physics, Beihang University,
Beijing 100191, China
4 Department of Nuclear Engineering, Texas A&M University, College Station, TX 77843, USA;
lshao@tamu.edu (L.S.); gigaxj@tamu.edu (J.G.)
* Correspondence: 20051702bx@163.com (X.B.); wusj@buaa.edu.cn (S.W.);
Tel.: +86-10-8231-6326 (S.W.); Fax: +86-10-8231-7108 (S.W.)

Academic Editor: Hugo F. Lopez

Received: 6 November 2016; Accepted: 10 January 2017; Published: 14 January 2017

Abstract: Specimens of the SA508-IV reactor pressure vessel (RPV) steel, containing 3.26 wt. % Ni
and just 0.041 wt. % Cu, were irradiated at 290 ◦ C to different displacement per atom (dpa) with
3.5 MeV Fe ions (Fe2+ ). Microstructure observation and nano-indentation hardness measurements
were carried out. The Continuous Stiffness Measurement (CSM) of nano-indentation was used to
obtain the indentation depth profile of nano-hardness. The curves showed a maximum nano-hardness
and a plateau damage near the surface of the irradiated samples, attributed to different hardening
mechanisms. The Nix-Gao model was employed to analyze the nano-indentation test results. It was
found that the curves of nano-hardness versus the reciprocal of indentation depth are bilinear.
The nano-hardness value corresponding to the inflection point of the bilinear curve may be used as a
parameter to describe the ion irradiation effect. The obvious entanglement of the dislocations was
observed in the 30 dpa sample. The maximum nano-hardness values show a good linear relationship
with the square root of the dpa.

Keywords: SA508-IV; displacement per atom (dpa); ion irradiation hardening; inflection point;
reactor pressure vessel (RPV) steel; nano-hardness

1. Introduction
With the increasing demands for high capacity and long design life of nuclear reactors, the
performance of existing reactor pressure vessel (RPV) steels is becoming less adequate. It is important
that new RPV steels should possess higher yield strength and fracture toughness, lower ductile to
brittle transition temperature, and excellent neutron irradiation embrittlement resistance. The SA508-IV
RPV steel studied in this work is a new generation RPV steel, with higher nickel content and lower
copper content, compared with SA508-III. Ni is well known for improving the low-temperature
cleavage toughness by decreasing the energy barrier of kink formation [1,2]. To determine the
performance of this steel under nuclear environments, it is necessary to investigate the effect of
irradiation doses on the microstructure evolution and the mechanical properties of this new type of
RPV steel. The microstructure of this SA508-IV steel is mainly martensite structure with retained
austenite, which could guarantee strength and toughness.
Neutron irradiation embrittlement of RPV steels causes the most severe damage during operation
of nuclear power stations. Due to the long-term damage production and the radioactivity of the
neutron irradiation, the real neutron irradiation experiments are limited and very difficult to carry out.

Metals 2017, 7, 25; doi:10.3390/met7010025 www.mdpi.com/journal/metals

Metals 2017, 7, 25 2 of 11

Instead, high-energy heavy ion irradiation has been extensively used to study the irradiation response
of the candidate RPV steel because of the simplicity of use, easier control of irradiation parameters,
reduction of cost, rapid damage production, and absence of induced radioactivity [3–6]. Ion irradiation
is one of the best methods for investigation of irradiation embrittlement [7], and provides a rapid
and flexible way to achieve high doses without the hazards induced by activation of the materials [8].
Furthermore, the displacement cascades induced by ion irradiation are similar to those induced by
neutron irradiation [9]. On the other hand, the disadvantages of ion irradiation are inhomogeneous
damage profiles and shallow irradiation depth compared to neutrons [10].
The purpose of this paper is to fully characterize the relationship between the measured
nano-indentation test results and the irradiation doses. The classic Nix-Gao model was used to
analyze the test results. Considering the limitation of ion-irradiation depth and sample size, the
nano-indentation test is a quite useful method for the study of the mechanical properties of irradiated
materials, which uses the recorded depth into the specimen of an indenter along with the applied
load to determine the area of contact and obtain the hardness of the test specimen [11]. The technique
Continuous Stiffness Measurement (CSM) offers a significant improvement in nano-indentation
testing [12]. Compared with the loading-unloading method used in the past, the CSM has the great
advantage of obtaining the depth profile with only a single indent. The irradiation hardening should
be related to the irradiated microstructural features, which commonly belong to two groups: solute
atom clusters and matrix damage [13].

2. Experimental Procedures

2.1. Testing Materials and Irradiation Conditions

The material used in this study is a new generation RPV steel SA508-IV, designed with high Ni
(3.26 wt. %) and low Cu (0.041 wt. %) content. The detailed chemical compositions are shown in
Table 1. The rolled steel underwent a heat treatment process of holding for 1.5 h at 920 ◦ C, followed by
water quenching (WQ) to room temperature (RT), re-heating to 650 ◦ C for 30 h and then water cooling
to RT, called the as-received state. Heavy ion irradiations were conducted with 3.5 MeV Fe ions (Fe2+ )
using the ion accelerator in the Texas A&M University (College Station, TX, USA) on these as-received
state samples, at 290 ± 5 ◦ C. The ion accelerator is shown in Figure 1. The Stopping and Ranges of
Ions in Matters (SRIM) was used for the irradiation damage calculation. The irradiation damage (D, in
dpa) could be calculated by the equation [14],

F · Nd1ion · Mmol
D= (1)
ρ · d · NA

in which, F is the ion fluence, in ion/cm2 ; Mmol is the target’s molar mass, in g/mol; NA is the
Avogadro’s constant.

Table 1. Chemical composition of SA508-IV Ni-Cr-Mo alloy steel in wt. %.

C Si Mn P S Ni Cr Cu Mo Al Fe
0.15 0.36 0.34 0.011 0.008 3.26 1.66 0.041 0.46 0.005 Balance

The displacement damage and ion distribution versus depth calculated by SRIM is shown in
Figure 2. It can be seen that the peak damage depth sits at around 1000 nm below the ion irradiated
surface. The ion distribution reaches the peak value at around 1200 nm depth.
Metals 2017, 7, 25 3 of 11
Metals 2017, 7, 25 3 of 11
Metals 2017, 7, 25 3 of 11

Figure 1. The picture of the ion accelerator.

Figure1.1.The
Figure Thepicture of the
picture of theion
ionaccelerator.
accelerator.

Figure 2. Depth profile of displacement per atom (dpa) and ion distribution in 3.5 MeV Fe2+ ion
Figure 2. Depth profile of displacement per atom (dpa) and ion distribution in 3.5 MeV
irradiation. Fe2+ ion
Figure 2. Depth profile of displacement per atom (dpa) and ion distribution in 3.5 MeV Fe2+ ion irradiation.
irradiation.
The corresponding dose calculation was done in pure Fe with the displacement energy Ed = 40
The corresponding
Thedose
corresponding dose calculation
dose was done inin
pure FeFewith the
thedisplacement energy EEdd==4040 eV.
eV. The and dose rate atcalculation
a depth ofwas 300done
nm were pureused with
for damage displacement
parameters. energy
The applied
The dose and
eV. The dose rate at a depth of 300 nm were used for damage parameters. The applied dose rate
dose ratedose
was and
fixeddoseat rate×at10a−3 depth
1.74 dpa/s of
at 300
the nm were
peak
−3 dpa/s at−3the peak or 0.7 × 10−3 dpa/s
or used
0.7 × 10for damage
−3 dpa/s at parameters.
the depth of Thenm.
300 applied
The
was fixed
doses at
dose rate 1.74
reached × 10
was fixed
1, 2, 3,at10,
1.7420,× 30
10 dpa,dpa/s at the peakAor
respectively. 0.7 ××10
6 mm
−3
6 mm at
dpa/sthe depth
ionatbeam
the depth of 300 nm.
of 300
was used in nm. The todoses
orderThe
reached 1, 2,
doses
ensure 3, 10,
reached
full 20,
1, 2,303,on
coverage dpa,
10, respectively.
the20, 30 dpa,The
samples. A 6 mm ×
respectively.
parameters 6 mm
A of mm ion
× 6 mmbeam
ion-irradiation was
ionarebeamused
shown wasin order
inused
Table in2.to ensure
order to full
ensure
coverage onfull
From coverage
theTable 2, it on
samples. the
The
can besamples.
seen thatThe
parameters parameters
30 of
dpa of ion-irradiation
ion-irradiation
of ion-irradiation areneeds
shown are
420 shown
inmin.
Table in
2. Tablethe
Although 2. 30 dpa
From
dosageFrom
Table Table
2, it2,can
of neutron it can
be be
seen
irradiation seenthatthat
needs 3030dpa
dpaof
hundreds ofion-irradiation
ion-irradiation
of needs
years in the neutronneeds420420min.
min.
reactor Although
service,the
in Although this30
the dpa
RPV30 dpa
dosagedosage
steel of
ofSA508-IVneutron irradiation
neutron isirradiation
designed for needs hundreds
the fourth-generation
needs of
hundreds of years years in
nuclear the
in the neutron
reactor reactor
where
neutron in service,
the neutron
reactor this RPV
flux inside
in service, this RPV
steelbeSA508-IV is designed for thethe fourth-generation nuclearitreactor where to the neutron flux inside
steel will
SA508-IV much is higher,
designed especially
for theinfourth-generation
fast reactor, therefore,
nuclear is essential
reactor where study
the the performance
neutron flux inside
will
of be much RPV
SA-508-IV higher, especially
steel underinhighin the fast reactor, therefore, it is essential to study the performance
will be much higher, especially thedosage.
fast reactor, therefore, it is essential to study the performance of
of SA-508-IV RPV steel under high dosage.
SA-508-IV RPV steel under high dosage.
Table 2. The parameters of ion-irradiation.
Table 2. The parameters of ion-irradiation.
dpa Table 2. The parameters
Fluence Duration (min)
of ion-irradiation.
dpa
1 Fluence
2.46 × 1015 Duration
14.01(min)
21 2.46 ×× 10
4.92 1015
15 14.01
28.02
dpa Fluence Duration (min)
32 4.92 ×× 10
1015 28.02
15
7.38 42.03
3 1 7.38
2.46 × × 10 15
15
14.01 42.03
10 2.46 × 16 140.1
10 2 4.92 15
2.46××× 1016
16
28.02 140.1
20 4.92 280.2
20
30 3 4.92××× 10
7.38
7.38 15
1016
16
42.03 280.2
420.3
30 10 2.46 1016
7.38×× 10 16
140.1 420.3
2.2. Microstructure Observation 20 4.92 × 1016 280.2
2.2. Microstructure Observation 30 7.38 × 1016 420.3
After ion-irradiation, the samples were cut from the sample center along the irradiation
AfterStandard
direction. ion-irradiation,
grindingthe
andsamples were
polishing was cut fromfollowed
applied, the sample center with
by etching along the%irradiation
5 vol nital. The
direction. Standard
2.2. Microstructure
microstructure grinding
Observation
of the andsamples
etched polishing wasexamined
was applied, followed
using theby etching
Quanta with
200F5 vol % nital.
Field The
Emission
microstructure Scanning
Environmental of the etched samples
Electron was (FEESEM)
Microscopy examined (FEI,
usingHillsboro,
the Quanta 200F Field Emission
OR, USA).
After ion-irradiation,
Environmental Scanningthe samples
Electron were cut (FEESEM)
Microscopy from the sample center along
(FEI, Hillsboro, the irradiation direction.
OR, USA).
Standard grinding and polishing was applied, followed by etching with 5 vol % nital. The microstructure
of the etched samples was examined using the Quanta 200F Field Emission Environmental Scanning
Electron Microscopy (FEESEM) (FEI, Hillsboro, OR, USA).
Metals 2017, 7, 25 4 of 11

Thin foils for TEM observation were prepared perpendicular to the irradiated surface4 using
Metals 2017, 7, 25 of 11
the
Zeiss Auriga Crossbeam focused ion beam (FIB) system (Zeiss, Jena, Germany). To remove defects
appearingThin underfoilsGaforimplantation at the
TEM observation FIBprepared
were preparation, the specimens
perpendicular were polished
to the irradiated surface by low-energy
using the
Zeiss Auriga
ion sputtering of Ar Crossbeam focused ion
ions accelerated beam
at 150 (FIB) system
V using (Zeiss, Jena, Germany).
an ultralow-energy To remove
Ar ion beam defects
sputtering system.
After appearing
sufficiently under Ga implantation
thinning, the samplesatwere
the FIB preparation,
observed the F20
using the specimens were polished
Field Emission by
Transmission
low-energy
Electron Microscopy ion sputtering
(FE-TEM)of(FEI,
Ar ions accelerated
Hillsboro, OR,atUSA).
150 V using an ultralow-energy Ar ion beam
sputtering system. After sufficiently thinning, the samples were observed using the F20 Field
Emission Transmission
2.3. Nano-Indentation Tests Electron Microscopy (FE-TEM) (FEI, Hillsboro, OR, USA).
The nano-indentation
2.3. Nano-Indentation Testshardness at room temperature was measured using a Nano Indenter XP
(MTS, EdenThePrairie, MN, USA)
nano-indentation with at
hardness a 2room diamond Berkovitch
µm temperature was measuredindenter
using a (three-sided
Nano Indenterpyramid)
XP
under(MTS,
a maximum load of 500 mN. The Continuous Stiffness Measure (CSM)
Eden Prairie, MN, USA) with a 2 μm diamond Berkovitch indenter (three-sided was used to study the
pyramid)
mechanical
under aproperties.
maximum loadThe depth (h) profiles
of 500 mN. of nano-hardness
The Continuous (H) up to
Stiffness Measure a depth
(CSM) wasof about
used 2000 nm
to study the were
mechanical
obtained properties.
using this The depth
CSM method (h) profiles
in the of nano-hardness
study. Five indentations(H) up to
were a depth
made of about
on each 2000
of the nm
specimens.
were obtained using this CSM method in the study. Five indentations were made on each of the
3. Results and Discussion
specimens.

3. Results and Discussion

3.1. Microstructure
In the
3.1. as-received state samples, the coarse carbides are mainly M23 C6 types, which were observed
Microstructure
in our previous work [15]. High density of fine M6 C carbides formed after the ion irradiation, which
In the as-received state samples, the coarse carbides are mainly M23C6 types, which were
were observed
supposedintoour form in the high-nickel RPV steels after irradiation [16,17]. In our recent study,
previous work [15]. High density of fine M6C carbides formed after the ion
the Cu-rich clusters
irradiation, which(CRCs) preferred
were supposed to to
formform under
in the low dose
high-nickel RPVirradiation (3 dpa) but
steels after irradiation disappeared
[16,17]. In
after our
highrecent
dosestudy,
(30 dpa), whereas
the Cu-rich Mo atoms
clusters (CRCs)started
preferredto to
segregate
form under onto
lowCr/Mn precipitates
dose irradiation to form
(3 dpa)
Cr/Mn/Mo until irradiated
but disappeared at high
after high dose dose (30 dpa)
(30 dpa), [18].Mo atoms started to segregate onto Cr/Mn
whereas
precipitates to form Cr/Mn/Mo until irradiated at high
The microstructures of samples after different ion-irradiation dose (30 dpa) [18].doses, 3 dpa, 10 dpa, 20 dpa,
The microstructures of samples after different
and 30 dpa, are shown in Figure 3a–d, respectively, from which ion-irradiation doses,it3 can
dpa, be
10 dpa,
seen20that
dpa, there
and are
no significant differences between the martensitic microstructure of the four differentlynodosed
30 dpa, are shown in Figure 3a–d, respectively, from which it can be seen that there are
significant differences between the martensitic microstructure of the four differently dosed
ion-irradiated samples. Thus it could be speculated that ion irradiation affects the density or size of
ion-irradiated samples. Thus it could be speculated that ion irradiation affects the density or size of
the nano-clusters/precipitates much more than grain size or phases structure.
the nano-clusters/precipitates much more than grain size or phases structure.

Figure 3. Microstructure of samples after different ion-irradiation doses, (a) 3 dpa; (b) 10 dpa; (c) 20 dpa;
and (d) 30 dpa.
Metals 2017, 7, 25 5 of 11

Figure 3. Microstructure of samples after different ion-irradiation doses, (a) 3 dpa; (b) 10 dpa; (c) 20
Metals dpa;
2017, and
7, 25(d) 30 dpa. 5 of 11

3.2. Nano-Hardness
3.2. Nano-Hardness
The indentation depth profiles of nano-hardness corresponding to different dpa are plotted in
FigureThe indentation
4 which depth profiles
demonstrates that the of nano-hardness
nano-hardnesscurves corresponding to different
of the irradiated dpa are
samples are plotted
related into
Figure 4 which demonstrates that the nano-hardness
the irradiation doses with the non-irradiated at the bottom and curves of the irradiated samples are
30 dpa irradiated at the top. It related
to
canthebeirradiation
seen that the doses with the non-irradiated
nano-hardness curve of each at the bottom
state sample and
canthe be30divided
dpa irradiated
into three at regions.
the top.
It
Thecannano-hardness
be seen that the nano-hardness
value goes up with curve of each
increase of state
depthsample canand
initially, be divided
reaches into three regions.
the highest value
The nano-hardness value goes up with increase of depth initially, and
near the surface (region A), and then goes down with the further penetration into the samples reaches the highest value near
the surface
(region B and(region
C inA), and then
Figure 4). Thegoes down with
variation the further
in region penetration
A is known as the into the samples
reverse (region
indentation B
size
and
effectC (RISE),
in Figure 4). Thethe
whereas variation
phenomenonin region in A
theis broader
known as the reverse
regions B andindentation
C (the decreasesize effect (RISE),
in hardness
whereas
with furtherthe phenomenon
depth) is calledin the
thebroader regions
indentation sizeBeffect
and C(ISE)
(the decrease
[19,20]. in hardness with further depth)
is called theregion
In the indentation
B, theresize
areeffect
plateau(ISE) [19,20].profiles in the low dose irradiation samples (1–3 dpa).
damage
In the region B, there are plateau
With the increase of the dosage, the plateau stage damage profiles in the (10
weakens lowdpa),
dose andirradiation samples (1–3
then disappears dpa).
(20 dpa),
With the increase
but shows of theindosage,
up again the 30the dpaplateau
sample.stage weakens (10the
Considering dpa),
CRCsand then
in the disappears
3 dpa sample (20 dpa), but
which
shows
disappearup again
in thein30thedpa
30 dpa sample.
sample, Considering
demonstrated in the
ourCRCs in thestudy
previous 3 dpa[18],
samplethe which
formation disappear
of CRCs in
the 30 dpa sample, demonstrated in our previous study [18], the formation
could be related to the appearance of the plateau stage (90–180 nm depth) in the nano-hardness of CRCs could be related
to the appearance
curves of the low of the plateau
irradiation dosestage (90–180The
samples. nmplateau
depth) in the nano-hardness
damage profile represents curvesthe of damage
the low
irradiation
saturation. dose samples.
Therefore, it The
could plateau damage profile
be concluded that the represents
hardening the effect
damage saturation.
after low doses Therefore,
of ion
it could be concluded that the hardening effect after low doses of ion
irradiation is because of the formation of CRCs, and the nano-hardness profiles reach the plateau irradiation is because of the
formation
stage due to of the
CRCs, and theofnano-hardness
saturation CRCs. Furthermore, profiles reach
there the plateau
is also an obvious stage due toprofile
plateau the saturation
(110–230
of CRCs. Furthermore, there is also an obvious plateau profile (110–230
nm depth region) in the 30 dpa sample. The hardening effect under higher dosage is probably nm depth region) in the
30 dpa sample.
caused The hardening
by the formation of theeffect under higherdislocation
interstitial-type dosage is probably
loops and caused by the formation
the Cr/Mn/Mo of the
precipitates.
interstitial-type
The plateau stage dislocation
of the 30 dpaloops and the
curve can Cr/Mn/Mo
be considered precipitates.
to result from Theloopplateau stage of [21].
coalescence the 30 Asdpa
for
curve can be considered to result from loop coalescence
the depth of the plateau stage, it could be seen in Figure 4 that [21]. As for the depth of the plateau
plateau stage in the 30 dpa stage, it
could
samplebeisseen in Figure
deeper 4 that
than that inthe
theplateau
low dose stage in the 30
samples. Thisdpa sample
could is deeper than
be explained that in the low
as accumulation of
dose samples.
irradiation Thisand
defects could be explained as
a move-forward accumulation
towards the innerofofirradiation
the samples defects and a move-forward
with increasing irradiation
towards
dose. the inner of the samples with increasing irradiation dose.

Figure 4.
Figure 4. Depth
Depth profiles
profiles of
of nano-hardness
nano-hardness of
of SA508-IV
SA508-IV after
after different
different ion-irradiation
ion-irradiation doses.
doses.

According to the Nix and Gao equation [22] for the ISE stage, which describes the relationship
According to the Nix and Gao equation [22] for the ISE stage, which describes the relationship
between nano-hardness (H) and depth (h),
between nano-hardness (H) and depth (h),
0.5
l∗
 
H = H0 1 + (2)
h
Metals 2017, 7, 25 6 of 11

0.5
  l*  
H  H 0 1     (2)
  h 
  
Metals 2017, 7, 25 6 of 11
where H is the hardness for a given depth of indentation h; H0 is the hardness at the limit of infinite
depth; l* is a characteristic length that depends on the shape of the indenter, the shear modulus and
where H is the hardness for a given depth of indentation h; H0 is the hardness at the limit of infinite
H0.
depth; l* is a characteristic length that depends on the shape of the indenter, the shear modulus and H0 .
The curves of the ISE stage (region B and C) in Figure 4 could be replotted in Figure 5. The
The curves of the ISE stage (region B and C) in Figure 4 could be replotted in Figure 5. The circled
circled area in Figure 5a is enlarged and shown in Figure 5b. There is a difference between the
area in Figure 5a is enlarged and shown in Figure 5b. There is a difference between the irradiated
irradiated samples and the non-irradiated sample (0 dpa). The slope of the non-irradiated curve
samples
remainsand the non-irradiated
constant samplewhile
in the ISE stage, (0 dpa).
theThe slope
slopes ofofthe
theirradiated
non-irradiatedonescurve
changeremains
at theconstant
critical
in the ISE stage,
indentation while
depth, the slopes
forming theofbilinear
the irradiated
curves.ones change at
According to the critical (2),
Equation indentation
H depth, forming
02 × l* is equal to the
the
slope bilinear
of thecurves.
curvesAccording
in Figure 5. to It
Equation
could be(2), H0 2 ×
found l* isthere
that equal areto not
the many
slope of the curvesbetween
differences in Figurethe5.
ItH0could that there are not many differences between the H0 and H0 irr unirr
irr andbe Hfound
0unirr, thus the ion irradiation affects l* dramatically. As stated in Equation (2), the l*
, thus the ion
irradiation affects l* dramatically. As stated in Equation (2), the l* depends
depends on the shape of the indenter, the H0 and the shear modulus. The effect of ion irradiation on the shape of the indenter,is
the H 0 and the shear modulus. The effect of ion irradiation is therefore
therefore mainly on the shear modulus of the materials. The C region in Figure 4 corresponds to themainly on the shear modulus
of the materials.
initial linear partThe of C theregion
curvesin in
Figure
Figure4 corresponds
5, which is notto the initial linear
significantly part of by
affected thethe
curves in Figure 5,
ion-irradiation.
which is not significantly affected by the ion-irradiation. The following
The following increased part of the irradiated curves in Figure 5 represents the region B (Figure increased part of the irradiated
4),
curves in Figure 5 represents the region B (Figure 4), which is the area
which is the area influenced mostly by the ion irradiation. The bilinear profile of the irradiated influenced mostly by the
ion irradiation.
samples in Figure The5bbilinear profile
is formed dueof tothe
theirradiated samples
soft substrate effectin(SSE)
Figureof 5b
theisdeeper
formed duejust
area to the soft
beneath
substrate effect (SSE) of
the irradiated depth area [20,22]. the deeper area just beneath the irradiated depth area [20,22].

Figure 5. H2 versus 1/h profile for the indentation size effect (ISE) region according to the Nix-Gao
Figure 5. H2 versus 1/h profile for the indentation size effect (ISE) region according to the Nix-Gao
model, the circled area in (a) is enlarged in (b).
model, the circled area in (a) is enlarged in (b).

From Equation (2) it could be found that the slope of the second line just after the inflection
From
point of the Equation
bilinear(2) it could
curves be found
in Figure 5b that the slope
is equal to H0of2 ×the second
l*. Thus line
the justthe
l* of after the inflection
irradiated stage point
could
of the bilinear curves in Figure 5b is equal to H 2 × l*. Thus the l* of the irradiated stage could be
0
be obtained by the slope divided by H0 for each state sample. The relationship between l* and dpa
2
obtained
is plottedby inthe slope6.divided
Figure In Figure by 6,H0it2 could
for eachbe state
seen sample.
that the The relationship
increase rate of l* between
is higher l* and dpalow
under is
plotted
dosage inthan
Figure
that6.under
In Figurehigh6, dosage,
it could be seen means
which that thethe increase of l* is higher
ratebecomes
l* value under
constant low dosage
when the ion
than under high dosage, which means the l*
irradiation dose is high enough for the irradiation effect on the nano-hardness toirradiation
that value becomes constant when the ion reach the
dose is highstate.
saturation enough for the irradiation effect on the nano-hardness to reach the saturation state.
Figure
Figure 4 shows
4 shows that
that each
each nano-hardness
nano-hardness curve curve has has aa maximum
maximum valuevalue which
which varies
varies with
with the
the
irradiation doses. The relationship between the maximum nano-hardness
irradiation doses. The relationship between the maximum nano-hardness and dpa is presented in and dpa is presented
in Figure
Figure 7. The
7. The dosedose dependence
dependence of maximum
of the the maximum nano-hardness
nano-hardness in Figure
in Figure 7a is similar
7a is similar to thattoofthat
the
of characteristic length l*
characteristic length l* as shown in Figure 6 which demonstrates a rapid increase at low dosesatand
the as shown in Figure 6 which demonstrates a rapid increase lowa
doses
slowdownand a ofslowdown
the rateofoftheincrease
rate of increase
at higher at higher
doses, doses, implying
implying that thethat irradiation
the irradiation effect
effect on
on nano-hardness would become saturated eventually after high dosage.
nano-hardness would become saturated eventually after high dosage. Zhang et al. [3] proposed a Zhang et al. [3] proposed
apower-law
power-lawdependence
dependenceofofthe thenano-hardness
nano-hardnesson on dpa.
dpa. InIn this
this work,
work, the
the maximum
maximum nano-hardness
nano-hardness
versus the square root of dpa in Figure 7b shows a linear increase relationship. The linear fitness
result is, p
Hmax = 12.26 + 2.09 dpa (3)
Metals 2017, 7, 25 7 of 11
Metals 2017, 7, 25 7 of 11
versus the square root of dpa in Figure 7b shows a linear increase relationship. The linear fitness
versusis,the square root of dpa in Figure 7b shows a linear increase relationship. The linear fitness
result
Metals 2017, 7, 25 7 of 11
result is,
H max  12.26  2.09 dpa (3)
H max  12.26  2.09 dpa (3)
where
where thethe constant
constant 12.26
12.26 is
is the
the peak
peak value
value ofof the
the nano-hardness
nano-hardness curve
curve for
for the
the non-irradiated
non-irradiated sample,
sample,
the
the coefficient
wherecoefficient 2.09
2.09can
the constant canbebeconsidered
12.26 the peak as
is considered thethe
value
as ion-irradiation
of the hardening
nano-hardness
ion-irradiation parameter,
curve
hardening which
forparameter, couldcould
the non-irradiated
which be used
sample,
be
theevaluate
to
used coefficient
to evaluate 2.09
thecan
the performancebe considered
of theof
performance theas
RPV thesteels
steels
RPV ion-irradiation
under under hardening parameter, which could be
irradiation.
irradiation.
used to evaluate the performance of the RPV steels under irradiation.

Figure 6. The relationship between the l* and dpa.

Figure 6. The relationship between the l* and dpa.
Figure 6. The relationship between the l* and dpa.

Figure 7. The relationship between the maximum nano-hardness and (a) dpa; (b) the square root of
Figure 7. The relationship between the maximum nano-hardness and (a) dpa; (b) the square root of
dpa.
Figure 7. The relationship between the maximum nano-hardness and (a) dpa; (b) the square root
dpa.
of dpa.
It can be seen in Figure 7 that the 3 dpa point remains higher up on the linear fitting line. Since
It can be seen
the precipitates or inclusters
Figure are
7 that the 3 dpa
formed point remains
in different stage higher
of the upFe2+onion theirradiation
linear fitting line. Since
process, the
the It can be seenorinclusters
precipitates Figure 7 are
thatformed
the 3 dpa inpoint remains
different higher
stage of up on
the Fe the
2+ ion linear fitting line.
irradiation Since the
process, the
hardening mechanisms should also be different from low dose to high dose. The CRCs
2+ ion irradiation process, the hardeningare known
precipitates
hardening or clusters are formed in different stage of the Fe
to form atmechanisms
low doses shouldand toalso be different
disappear from doses
at high low dose to high dose.
[18,23–25], The CRCsetareal.known
and Bohmert have
mechanisms
to form at should
low also and
doses be different
to from low
disappear at dose
high todoses
high dose. The CRCs
[18,23–25], and are knownettoal.
Bohmert form at
have
demonstrated that the increase in hardness has good correlation with the square root of the volume
low doses
demonstrated and to disappear at high doses [18,23–25], and Bohmert et al. have demonstrated that the
fraction of the that theatom
solute increase in hardness
clusters hasitgood
[26]. Thus, could correlation with the
be speculated thatsquare
the firstroot of the volume
hardening stage
increase
fraction in the
hardness has good correlation with itthe square speculated
root of the volume fraction of the solute
could beof solute
attributed toatom clusters
the formation [26]. Thus,
of the CRCs.could
Frombe the plateau damage that theprofile
first hardening
of the 3 dpa stage
in
atom
could clusters
be [26]. Thus,
attributed to theitformation
could be speculated
of the CRCs.thatFrom
the first
the hardening
plateau stage profile
damage could be of attributed
the 3 dpa to
in
Figure 4 and the higher maximum nano-hardness point of 3 dpa in Figure 7, it can be concluded
the formation
Figure of the CRCs. From the plateau damage profile of the 3 dpa in Figure 4 and the higher
that the4formation
and the higher
of CRCs maximum
becomes nano-hardness
saturated whenpoint the doseof 3ofdpa in Figure
irradiation 7, it can
reaches be concluded
3 dpa. When the
maximum
that the nano-hardness
formation of CRCs point
becomesof 3 dpa in Figure
saturated when 7, it
the can be concluded
dose of irradiation thatreaches
the formation
3 dpa. of CRCs
When the
dose increases to 10 or 20 dpa, the hardening mechanism changes from the CRCs to the precipitates,
becomes saturated when the dose of irradiation reaches 3 dpa. When the dose
dose increases to 10 or 20 dpa, the hardening mechanism changes from the CRCs to the precipitates, increases to 10 or 20 dpa,
the hardening mechanism changes from the CRCs to the precipitates, such as the Cr/Mn/Mo, and
different dislocation structures. The large scatter of 1 and 10 dpa data found from Figure 7b may be
because of the variety of the microstructures or the surface condition.
Metals 2017, 7, 25 8 of 11
Metals 2017, 7, 25 8 of 11
such as the Cr/Mn/Mo, and different dislocation structures. The large scatter of 1 and 10 dpa data
found from Figure 7b may be because of the variety of the microstructures or the surface condition.
The TEM observation results of the dislocations in the 3 dpa and 30 dpa samples are shown in
The TEM observation results of the dislocations in the 3 dpa and 30 dpa samples are shown in
Figure 8. It can be seen that the dislocations in the 3 dpa irradiated sample (Figure 8a) are mainly
Figure 8. It can be seen that the dislocations in the 3 dpa irradiated sample (Figure 8a) are mainly
parallel and along the directions of ion irradiation. In contrast, in Figure 8b, the dislocations are found
parallel and along the directions of ion irradiation. In contrast, in Figure 8b, the dislocations are
to be entangled with one other. Y. Takayama et al. [27] found that nickel element addition enhances the
found to be entangled with one other. Y. Takayama et al. [27] found that nickel element addition
irradiation hardening of RPV steel during the irradiation process. Ni and Mn elements are reported to
enhances the irradiation hardening of RPV steel during the irradiation process. Ni and Mn elements
have the tendency to promote the formation of interstitial loops during irradiation [28–30] and the high
are reported to have the tendency to promote the formation of interstitial loops during irradiation
dose of irradiation could generate high density of self-interstitial atoms by the cascade effect which
[28–30] and the high dose of irradiation could generate high density of self-interstitial atoms by the
results in the formation of interstitial-type dislocation loops [31,32]. Therefore, it can be considered
cascade effect which results in the formation of interstitial-type dislocation loops [31,32]. Therefore,
that thebeentanglement
it can of the
considered that dislocations
the entanglementand the interstitial-type
of the dislocations dislocation loops are one of
and the interstitial-type the main
dislocation
factors responsible for the hardening effect after high dose irradiation.
loops are one of the main factors responsible for the hardening effect after high dose irradiation.

Figure 8. Dislocation density of different dose ion-irradiation samples, (a) 3 dpa; (b) 30 dpa.
Figure 8. Dislocation density of different dose ion-irradiation samples, (a) 3 dpa; (b) 30 dpa.

In Figure 4, it can be seen that there are multiple discontinuous displacement bursts occurring
In Figure
clearly in the4, nano-hardness
it can be seen that there depth
versus are multiple
curvesdiscontinuous displacementsamples.
of some ion-irradiated bursts occurring
Such a
clearly in the nano-hardness
non-uniform versus depth
displacement response named curves of some
“pop-in” is ion-irradiated
marked by arrows samples. Such a non-uniform
in Figures 4 and 5. The
displacement
pop-ins on theresponse
1 dpa curvenamed “pop-in”
occur around is marked
25–50 nm by arrows in Figuresthe
depth, whereas 4 and
one 5.onThethepop-ins
10 dpaon the
curve
1stays
dpa curve occur around 25–50 nm depth, whereas the one on the 10
around 85 nm depth. Generally, the occurrence of pop-in phenomenon in metals can be dpa curve stays around 85 nm
depth. Generally,
attributed the occurrence
to several factors such of pop-in phenomenon
as dislocation in metals
nucleation andcan be attributed
propagation, to several
crack factors
formation or
such as dislocation nucleation
phase transformation [33–36]. and propagation, crack formation or phase transformation [33–36].
The
The pop-ins
pop-ins on on nano-hardness
nano-hardness curves curves ofof the
the SA508-IV
SA508-IV steel steel samples
samples in in this
this study
study probably
probably
occurred due to the transformation of the retained austenite to martensite. During
occurred due to the transformation of the retained austenite to martensite. During the measurement the measurement of
the nano-hardness along the depth of the sample, the indenter may encounter
of the nano-hardness along the depth of the sample, the indenter may encounter the retained the retained austenite.
Because
austenite.the retainedthe
Because austenite
retainedis austenite
relatively issoft, the corresponding
relatively nano-hardness
soft, the corresponding is lower which
nano-hardness is
results in the drop of the nano-hardness on the curve. On the other hand,
lower which results in the drop of the nano-hardness on the curve. On the other hand, the plastic the plastic deformation
of the retained
deformation of austenite
the retained mayaustenite
induce transformation of the austeniteoftothe
may induce transformation martensite
austenitewhich is much
to martensite
harder
which than the retained
is much harder than austenite. Thus the
the retained nano-hardness
austenite. Thus the in the hardness-depth
nano-hardness curve
in the will increase,
hardness-depth
therefore, forming the pop-ins on the curves. Whether there are pop-ins on
curve will increase, therefore, forming the pop-ins on the curves. Whether there are pop-ins on the curves depends on the
the
distribution
curves depends of theonretained austenite. of
the distribution If there are retained
the retained austenite
austenite. grains
If there arealong the measuring
retained depth
austenite grains
of the sample,
along pop-insdepth
the measuring wouldofbethegenerated, otherwise,
sample, pop-ins therebe
would would be no pop-ins.
generated, otherwise, there would be
Attention
no pop-ins. should be paid to the inflection points of the bilinear curves (the crossing points of
the two-line
Attention curves)
should in be
Figure
paid5b,
to corresponding to theof
the inflection points cut-off point between
the bilinear curves (theB region and points
crossing C region
of
(Figure 4). The indentation depths at the inflection points are similar for the
the two-line curves) in Figure 5b, corresponding to the cut-off point between B region and C region irradiated samples, but
the nano-hardness
(Figure value increases
4). The indentation depths with
at thethe increasepoints
inflection of theareirradiation
similar for dosage. As mentioned
the irradiated above,
samples, but
Metals 2017, 7, 25 9 of 11

the bilinear profile is attributed to the SSE of the non-irradiated area just beneath the irradiated area.
Therefore, the nano-hardness value (Hinf ) and the indentation depth (hirr/unirr ) corresponding to the
inflection point, can be considered as a parameter representing the irradiation mostly affected layer on
the surface of the material, and below this layer, the effect of irradiation can be neglected.
The nano-hardness profiles in Figure 4 manifest when the measuring depth is over 1500 nm, the
nano-hardness value remains almost constant. Therefore, to measure the nano-hardness as a property
of a material, the indentation depth must be greater than 1500 nm. The nano-hardness value at a depth
of ~2000 nm is taken as the material nano-hardness property in normal practice. To characterize the
effect of ion irradiation on the nano-hardness of a material, however, different parameters should
be applied since the effect of ion irradiation is limited within the surface thin layer of the material.
As discussed above, the maximum nano-hardness value Hmax or the hardness value corresponding
to the inflection point (Hinf ) could be used to describe the irradiation effect on the nano-hardness
of materials.

4. Conclusions
The heavy ion irradiation process was demonstrated to produce a similar cascade effect to neutron
irradiation. Micro-mechanical properties were obtained by nano-hardness tests. Based on the above
analysis, conclusions can be drawn as follows:

(1) The CSM nano-hardness profiles of the irradiated SA508-IV steel samples exhibit a maximum
value and a plateau.
(2) The maximum nano-hardness (Hmax ) increases rapidly at low doses and slowly at higher doses.
The relationship between Hmax and dpa follows a 1/2-power law.
(3) The inflection point of the bilinear curve is the point separating the B region and C region on the
CSM nano-hardness profile. Beyond the inflection point, the ion irradiation effect on the materials
is insignificant.
(4) The characteristic length l* which is affected by ion-irradiation was obtained by fitting the bilinear
curves, and also had a relationship with the displacement per atom (dpa).

Acknowledgments: This work is financially supported by the National Science and Technology Key Specific
Project: Life Management Technology of Nuclear Power Plant of China (Grant No. 2011ZX06004-002). The authors
would like to express thanks for the help with ion-irradiation experiments conducted in the Department of Nuclear
Engineering in Texas A&M University (USA).
Author Contributions: Xue Bai designed the research, conducted the experiments, and then finished the draft of
this paper, Sujun Wu and Peter K. Liaw supervised the project and help revised the manuscript, Lin Shao and
Jonathan Gigax helped with the ion-irradiation experiments, all authors reviewed the manuscript.
Conflicts of Interest: The authors declare no conflicts of interest.

References
1. Chen, Y.T.; Atteridge, D.G.; Gerberich, W.W. Plastic flow of Fe-binary alloys-I. A description at low
temperatures. Acta Metall. 1981, 29, 1171–1185. [CrossRef]
2. Gerberich, W.W.; Chen, Y.T.; Atteridge, D.G.; Johnson, T. Plastic flow of Fe-binary alloys-II. Application of
the description to the ductile-brittle transition. Acta Metall. 1981, 29, 1187–1201. [CrossRef]
3. Zhang, H.; Zhang, C.; Yang, Y.; Meng, Y.; Jang, J.; Kimura, A. Irradiation hardening of ODS ferritic steels
under helium implantation and heavy-ion irradiation. J. Nucl. Mater. 2014, 455, 349–353. [CrossRef]
4. Liu, P.P.; Bai, J.W.; Ke, D.; Wan, F.R.; Wang, Y.B.; Wang, Y.M.; Ohnuki, S.; Zhan, Q. Effects of deuterium
implantation and subsequent electron irradiation on the microstructure of Fe-10Cr model alloy. J. Nucl. Mater.
2012, 423, 47–52. [CrossRef]
5. Klueh, R.L.; Gelles, D.S.; Jitsukawa, S.; Kimura, A.; Odette, G.R.; van der Schaaf, B.; Victoria, M.
Ferritic/martensitic steels-overview of recent results. J. Nucl. Mater. 2002, 307, 455–465. [CrossRef]
Metals 2017, 7, 25 10 of 11

6. Zhang, C.H.; Sun, Y.M.; Song, Y.; Shibayama, T.; Jin, Y.F.; Zhou, L.H. Defect production in silicon carbide
irradiated with Ne and Xe ions with energy of 2.3 MeV/amu. Nucl. Instrum. Methods Phys. Res. B 2007, 256,
243–247. [CrossRef]
7. Fujii, K.; Fukuya, K.; Hojo, T. Effects of dose rate change under irradiation on hardening and microstructural
evolution in A533B steel. J. Nucl. Sci. Technol. 2013, 50, 160–168. [CrossRef]
8. Zhang, Z.W.; Liu, C.T.; Wang, X.L.; Miller, M.K.; Ma, D.; Chen, G.; Williams, J.R.; Chin, B.A. Effects of proton
irradiation on nanocluster precipitation in ferritic steel containing fcc alloying additions. Acta Mater. 2012,
60, 3034–3046. [CrossRef]
9. Was, G.S.; Busby, J.T.; Allen, T.; Kenik, E.A.; Jenssen, A.; Bruemmer, S.M.; Gan, J.; Edwards, A.D.; Scott, P.M.;
Andresen, P.L. Emulation of neutron irradiation effects with protons: Validation of principle. J. Nucl. Mater.
2002, 300, 198–216. [CrossRef]
10. Liu, P.P.; Wan, F.R.; Zhan, Q. A model to evaluate the nano-indentation hardness of ion-irradiated materials.
Nucl. Instrum. Methods Phys. Res. B 2015, 342, 13–18. [CrossRef]
11. Fischer-Cripps, A.C. Nanoindentation Testing, Nanoindentation; Springer: Berlin, Germany, 2011.
12. Li, X.D.; Bhushan, B. A review of nanoindentation continuous stiffness measurement technique and its
applications. Mater. Charact. 2002, 48, 11–36. [CrossRef]
13. Fujii, K.; Fukuya, K.; Hojo, T. Concomitant formation of different nature clusters and hardening in reactor
pressure vessel steels irradiated by heavy ions. J. Nucl. Mater. 2013, 443, 378–385. [CrossRef]
14. Hengstler-Eger, R.M.; Baldo, P.; Beck, L.; Dorner, J.; Ertl, K.; Hoffmann, P.B.; Hugenschmidt, C.; Kirk, M.A.;
Petry, W.; Pikart, P.; et al. Heavy ion irradiation induced dislocation loops in AREVA’s M5 alloy. J. Nucl. Mater.
2012, 423, 170–182. [CrossRef]
15. Bai, X.; Wu, S.; Liaw, P.K. Influence of thermo-mechanical embrittlement processing on microstructure and
mechanical behavior of a pressure vessel steel. Mater. Des. 2016, 89, 759–769. [CrossRef]
16. Klueh, R.L.; Hashimoto, N.; Sokolov, M.A.; Shiba, K.; Jitsukawa, S. Mechanical properties of
neutron-irradiated nickel-containing martensitic steels: I. Experimental study. J. Nucl. Mater. 2006, 357,
156–168. [CrossRef]
17. Klueh, R.L.; Hashimoto, N.; Sokalov, M.A.; Maziasz, P.J.; Shiba, K.; Jitsukawa, S. Mechianical properties of
neutron-irradiated nickel-containing martensitic steels: II. Review and analysis of helium-effects studies.
J. Nucl. Mater. 2006, 357, 169–182. [CrossRef]
18. Bai, X.; Wu, S.; Liaw, P.K.; Shao, L.; Gigax, J.; Wei, L. Effect of ion irradiation on microstructure and
nano-hardness of the SA508-IV reactor pressure vessel steel. Sci. Rep. submitted for publication. 2017.
19. Pharr, G.M.; Herbert, E.G.; Gao, Y. The indentation size effect: A critical examination of experimental
observations and mechanistic interpretations. Annu. Rev. Mater. Res. 2010, 40, 271–292. [CrossRef]
20. Kasada, R.; Takayama, Y.; Yabuuci, K.; Kimura, A. A new approach to evaluate irradiation hardening of
ion-irradiated ferritic alloys by nano-indentation techniques. Fusion Eng. Des. 2011, 86, 2658–2661. [CrossRef]
21. Jiang, J.; Wu, Y.C.; Liu, X.B.; Wang, R.S.; Nagai, Y.; Inoue, K.; Shimizu, Y.; Toyama, T. Microstructural evolution
of RPV steels under proton and ion irradiation studied by positron annihilation spectroscopy. J. Nucl. Mater.
2015, 458, 326–334. [CrossRef]
22. Nix, W.D.; Gao, H. Indentation size effects in crystalline materials: A law for strain gradient plasticity.
J. Mech. Phys. Solids 1998, 46, 411–425. [CrossRef]
23. Yabuuchi, K.; Yano, H.; Kasada, R.; Kishimoto, H.; Kimura, A. Dose dependence of irradiation hardening of
binary ferritic alloys irradiated with Fe3+ ions. J. Nucl. Mater. 2011, 417, 988–991. [CrossRef]
24. Akamatsu, M.; van Duysen, J.C.; Pareige, P.; Auger, P. Experimental evidence of several contributions to the
radiation damage in ferritic alloys. J. Nucl. Mater. 1995, 225, 192–195. [CrossRef]
25. Tobita, T.; Suzuki, M.; Iwase, A.; Aizawa, K. Hardening of Fe-Cu alloys at elevated temperatures by electron
and neutron irradiaions. J. Nucl. Mater. 2001, 299, 267–270. [CrossRef]
26. Bohmert, J.; Viehrig, H.-W.; Ulbricht, A. Correlation between irradiation-induced changes of microstructural
parameters and mechanical properties of RPV steels. J. Nucl. Mater. 2004, 334, 71–78. [CrossRef]
27. Takayama, Y.; Kasada, R.; Sakamoto, Y.; Yabuuchi, K.; Kimura, A.; Ando, M.; Hamaguchi, D.; Tanigawa, H.
Nanoindentation hardness and its extrapolation to bulk-equivalent hardness of F82H steels after single- and
dual-ion beam irradiation. J. Nucl. Mater. 2013, 442, S23–S27. [CrossRef]
Metals 2017, 7, 25 11 of 11

28. Nishiyama, Y.; Onizawa, K.; Suzuki, M.; Anderegg, J.W.; Nagai, Y.; Toyama, T.; Hasegawa, M.;
Kameda, J. Effects of neutron-irradiation-induced intergranular phosphorus segregation and hardening on
embrittlement in reactor pressure vessel steels. Acta Mater. 2008, 56, 4510–4521. [CrossRef]
29. Shibamoto, H.; Kitao, K.; Matsui, H.; Hasegawa, M.; Yamaguchi, S.; Kimura, A. Effects of Radiation on Materials,
20th International Symposium, ASTM STP 1405; Rosinski, S.T., Grossbeck, M.L., Allen, T.R., Kumar, A.S., Eds.;
American Society for Testing and Materials: West Conshohocken, PA, USA, 2001; p. 722.
30. Watanabe, H.; Arase, S.; Yamamoto, T.; Wells, P.; Onishi, T.; Odette, G.R. Hardening and microstructural
evolution of A533b steels irradiated with Fe ions and electrons. J. Nucl. Mater. 2016, 471, 243–250. [CrossRef]
31. Liu, P.P.; Zhao, M.Z.; Zhu, Y.M.; Bai, J.W.; Wan, F.R.; Zhan, Q. Effects of carbide precipitate on the mechanical
properties and irradiation behavior of the low activation martensitic steel. J. Alloy. Compd. 2013, 579, 599–605.
[CrossRef]
32. Radiguet, B.; Pareige, P.; Barbu, A. Irradiation induced clustering in low copper or copper free ferritic model
alloys. Nucl. Instrum. Methods Phys. Res. B 2009, 267, 1496–1499. [CrossRef]
33. Qian, X.; Han, L.; Zhang, W.; Gu, J. Nano-indentation investigation on the mechanical stability of individual
austenite in high-carbon steel. Mater. Charact. 2015, 110, 86–93.
34. Kim, B.; Trang, T.T.T.; Kim, N.J. Deformation behavior of ferrite-austenite duplex high nitrogen steel.
Met. Mater. Int. 2014, 20, 35–39. [CrossRef]
35. Mistra, R.D.K.; Zhang, Z.; Jia, Z.; Venkat Surya, P.K.C.; Somani, M.C.; Karjalainen, L.P.
Nanomechanical insights into the deformation behavior of austenitic alloys with different stacking fault
energies and austenitic stability. Mater. Sci. Eng. A 2011, 528, 6958–6963. [CrossRef]
36. Bahr, D.F.; Kramer, D.E.; Gerberich, W.W. Non-linear deformation mechanisms during nano-indentation.
Acta Mater. 1998, 46, 3605–3617. [CrossRef]

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