materials

Article
The Effect of the Static Load in the UNSM Process on
the Corrosion Properties of Alloy 600
Ki Tae Kim and Young Sik Kim *
Research Center for Energy and Clean Technology, School of Materials Science and Engineering,
Andong National University, 1375 Gyeongdong-ro, Andong, Gyeongbuk 36729, Korea;
kitae1@pyunji.andong.ac.kr
* Correspondence: yikim@anu.ac.kr; Tel.: +82-54-820-5504




Received: 3 September 2019; Accepted: 20 September 2019; Published: 27 September 2019


Abstract: To suppress stress corrosion-cracking, compressive residual stresses, such as shot peening,
laser peening, water jet peening, ultrasonic peening, and ultrasonic nanocrystal surface modification
(UNSM) are utilized. However, among the numerous techniques, there is little research about
the corrosion effect of detailed conditions, such as static load or amplitude in UNSM. A study on
UNSM among various techniques of adding compressive residual stress to Alloy 600 was conducted.
The focus of this study was on the effect of the static load in UNSM on the corrosion properties of Alloy
600. Microstructure analysis was conducted using an optical microscope (OM), a scanning electron
microscope (SEM), and electron backscattering diffraction (EBSD), while compressive residual stress
was measured using a nano-indentation technique. A cyclic polarization test and the AC (Alternating
Current)-impedance measurement were both used to analyze the corrosion properties. An increase in
static load under critical static load enhanced the grain boundary diffusion, consequently strengthened
the passive film, and facilitated the surface diffusion, thereby improving the passivation of Alloy
600. However, higher static loads over the critical value can lead to an increase in the friction
between the striking tip and the surface, thereby creating an overlapped wave, which reduces the
corrosion properties.

Keywords: alloy 600; UNSM; corrosion; static load; residual stress

1. Introduction
Ni alloy is among the fcc (face centered cubic) crystal structures; it has good strength, ductility,
resistance to corrosion, and oxidation resistance at high temperatures [1]. Therefore, it is commonly
used as a nuclear power plant material because of its high temperature corrosion and high temperature
strength. Alloy 600 and Alloy 690 are used in nuclear reactors and steam generators in the nuclear
power plants’ primary system [2,3]. There are reports that Alloy 600 is susceptible to primary water
stress corrosion cracking in field applications [4–7], hence Alloy 690 has been used for new plants
or as a replacement material for the Alloy 600. However, Alloy 600 is used in majority of the plants.
SCC (stress corrosion cracking) constitutes the major damage due to Alloy 600, and the damaged
areas include the CMDR (control rod drive mechanism) nozzle of the reactor head, the BMI (bottom
mounted instrumentation) nozzle of the reactor bottom, a dissimilar metal weld of the RPV (reactor
pressure vessel) nozzle, and the heat transfer tube of the steam generator [8].
There are many techniques to mitigate the stress corrosion cracking of Alloy 600, which include
substitution with high corrosion resistant materials, modification of water chemistry, and reduction
of residual stress. Among these remedies, the reduction of residual stress, including tensile stress
and compressive stress, can be achieved through surface treatment. Techniques used for adding
compressive residual stresses to materials include: shot peening [9–11], laser peening [12–16], water jet

Materials 2019, 12, 3165; doi:10.3390/ma12193165 www.mdpi.com/journal/materials

Materials 2019, 12, 3165 2 of 14

peening [17,18], ultrasonic peening [19,20], and ultrasonic nanocrystal surface modification (UNSM),
with many studies still ongoing. Water jet peening and laser peening have been used to mitigate SCC,
since 2001 and 2004, respectively. In the USA, nuclear power plants, such as Byron-2, Braidwood-1,
Wolf Creek and ANO-1 in 2016; and Callaway, Byron-1, Braidwood-2, and ANO-2 in 2017–2018 used
laser peening, and further research has been conducted in this regard [2].
Regarding the UNSM process, the material is impacted with a hard, rigid pin moving at an
ultrasonic frequency, typically 20 kHz. A tungsten carbide (WC) tip is then attached to an ultrasonic
horn, which strikes the specimen surface at about 20,000 times per second with 1000 to 10,000 shots
made per square millimeter within a very short time. This impact deforms the surface of the target
material and converts its microstructure into nanocrystals. The plastic deformation produces a 1–2 mm
deep compressive residual stress field in the material. The combination of surface deformation, the
nanostructured layer, and compressive residual stresses causes a delay in fatigue crack initiation [21].
The UNSM process consists of various variables, including static load, amplitude, pitch,
tip diameter, speed, etc. Numerous studies have been performed using limited conditions among
UNSM process. The reported effects of UNSM on the mechanical properties and microstructure can be
summarized as follows [22–26]: (i) The microstructure of the surface and under surface is converted
to a nanograined microstructure which enhanced yield strength, tensile strength, and hardness as
a result of the Hall–Pitch strengthening mechanism. (ii) Very high levels of compressive residual
stresses were formed (about (1–2 GPa). High compressive residual stress enhanced the resistance
to abrasion, wear, and fatigue lifetime. (iii) A new phase was formed—in an austenitic stainless
steel, martensite can be formed through a UNSM process and the formed martensite phase in turn
protects the formation of the necking, since the new phase increases the interface strength between
the inside matrix and the nanograined surface. (iv) Surface roughness can also be improved. On the
other hand, UNSM has influenced the corrosion properties as follows [27–31]: (i) Since the UNSM
process strengthens the passive film, the pitting corrosion resistance of austenitic stainless steels can
be enhanced. (ii) UNSM treatment of aged, austenitic stainless steel reduced chromium carbide and
carbon segregation, hence improving the inter-granular corrosion resistance. (iii) Introduction of high
compressive residual stress enhanced the resistance to SCC. Additionally, many studies about the
UNSM’s effect on Ti alloys and carbon steel have been performed. However, there is little research on
the detailed conditions, such as static load or amplitude, among UNSM conditions.
Therefore, this work focused on the effect of the static load to the surface via UNSM on the
corrosion properties of Alloy 600. The effects of the static load on the corrosion properties were
discussed on the basis of the microstructure, hardness, and residual stress.

2. Materials and Methods

2.1. Specimen
Alloy 600 was utilized for this study. Table 1 shows the chemical composition of the experimental
alloy. Heat treatment was applied to the specimen at 1040 ◦ C for 7 min. UNSM treatment was applied to
the surface using the UNSM equipment (Design Mecha-LM20 UNSM system, Asan, Korea). The UNSM
process is schematically presented in Figure 1 and UNSM treatment conditions are summarized as
in Table 2. The surface preceding the UNSM treatment was ground with #2000 SiC abrasive paper.
As illustrated in Figure 1, UNSM treatment was applied in a zig-zag manner and 2.38 mm tungsten
carbide tip was used with an amplitude of 30 µm and a pitch of 0.07 mm, as summarized in Table 2.
This work controlled the static load—10 N, 30 N, and 50 N.

Table 1. Chemical composition of Alloy 600 used in the experiments (wt. %). (This chemical composition
is provided by the manufacturer).

Ni Cr Fe C Mn S Si Cu
73.13 16.35 9.42 0.07 0.21 0.002 0.29 0.01
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Figure 1. Schematic of the ultrasonic nanocrystal surface modification (UNSM) process.

Figure 1. Schematic of the ultrasonic nanocrystal surface modification (UNSM) process.
Table 2. UNSM conditions for Alloy 600.
Table 2. UNSM conditions for Alloy 600.
Sample Name Static Load (N) Amplitude (µm) Pitch (mm) Tip Diameter(mm)
Sample Name
Untreated Static Load
- (N) Amplitude - (μm) Pitch -(mm) Tip Diameter(mm)
-
Untreated
10 N -10 -30 -
0.07 - 1)
2.38 (WC
1030
NN 1030 3030 0.07
0.07 2.38 (WC)
(WC1)
30 NN
50 3050 3030 0.07
0.07 2.38 (WC)
2.38 (WC)
1 WC: Tungsten Carbide.
50 N 50 30 0.07 2.38 (WC)
1 WC: Tungsten Carbide.
2.2. Microstructure Analysis
2.2. Microstructure Analysiswas observed through optical microscopy (AXIOTECH 100HD, ZEISS,
The microstructure
Oberkochen, Germany), was
The microstructure and observed
the surface profile optical
through was obtained with (AXIOTECH
microscopy the use of a 100HD,
3D microscopy
ZEISS,
(KH-7700, HiROX, Tokyo, Japan). Furthermore, the surface shape was observed
Oberkochen, Germany), and the surface profile was obtained with the use of a 3D microscopy by SEM (VEGA(KH-
II LMU,
7700, Tescan,
HiROX, Brno,Japan).
Tokyo, CzechFurthermore,
Republic) after
thethe UNSM
surface process.
shape Microstructural
was observed by SEM properties were
(VEGA II LMU,
analyzed using EBSD (Electron Backscattering Diffraction, Lyra 3 XMH, Oxford Ins.,
Tescan, Brno, Czech Republic) after the UNSM process. Microstructural properties were analyzed Abingdon, UK).
Specimens for EBSD analysis were ground using #4000 SiC paper, and then polished
using EBSD (Electron Backscattering Diffraction, Lyra 3 XMH, Oxford Ins., Abingdon, UK). using a colloidal
silica (0.04 µm).
Specimens for EBSDThe analysis
EBSD step sizeground
were was 0.3using
µm and theSiC
#4000 observed datathen
paper, and werepolished
post-processed
using a using the
colloidal
HKL channel 5 (Oxford Ins., Abingdon, UK) analysis software. The crystallographic
silica (0.04 μm). The EBSD step size was 0.3 μm and the observed data were post-processed using the structure and
latticechannel
HKL plane spacing
5 (OxfordwereIns.,
analyzed by XRD
Abingdon, UK)(X-ray diffraction)
analysis (Ultima
software. IV, Rigaku, Tokyo,
The crystallographic Japan) and
structure and
the scan rate was 1 ◦ /min.
lattice plane spacing were analyzed by XRD (X-ray diffraction) (Ultima IV, Rigaku, Tokyo, Japan)
and the scan rate
2.3. Hardness and was 1°/min.
Residual Stress Measurements
The samples’
2.3. Hardness hardnesses
and Residual were
Stress measured using a micro-Vickers hardness tester (HV-100, Mitutoyo,
Measurements
kawasakishi, Japan). Residual stress was determined using a nanoindentation system (Inforce 1000,
KLA,The samples’
Milpitas, USA)hardnesses were measured
with a Berkovich using
indenter with a micro-Vickers
a maximum hardness
load of 100 mN andtester (HV-100,
a holding time
Mitutoyo, kawasakishi, Japan). Residual stress was determined using a nanoindentation
of 10 s. An average of 10 measurements were used for each reported data point. system
(Inforce 1000, KLA, Milpitas, USA) with a Berkovich indenter with a maximum load of 100 mN and
a2.4.
holding time of 10Tests
Electrochemical s. An average of 10 measurements were used for each reported data point.

The corrosion test was performed in a solution of 1% NaCl at 30 ◦ C using a potentiostat (interface
2.4. Electrochemical Tests
1000, Gamry, Warminster, VA, USA). The saturation calomel electrode (SCE) was used as the reference
The corrosion
electrode, test was performed
while a high-density in arod
graphite solution of 1% NaCl
was utilized at counter
as the 30 °C using a potentiostat
electrode. (interface
De-aeration was
1000, Gamry, Warminster, VA, USA). The saturation
done using N2 gas at the rate of 100 mL/min for 30 min. calomel electrode (SCE) was used as the
reference electrode, while a high-density graphite rod was utilized as the counter electrode. De-
2.4.1. Cyclic
aeration was Polarization
done using N Test
2 gas at the rate of 100 mL/min for 30 min.

The specimen was coated with epoxy apart from a distance 1 cm2 after epoxy mounting. In the
2.4.1. Cyclic Polarization Test
cyclic polarization test, the forward and reverse scan rates were both 0.33 mV/s. Additionally, the cyclic
The specimen
polarization was coated
apex current densitywith
wasepoxy apart2 .from
0.1 mA/cm a distance
In the 1 cm2 after epoxy
forward polarization, mounting.
passive In the
current density
cyclic polarization
and pitting test,
potential theobtained,
were forward and reverse scan rates
the protection were was
potential bothdefined
0.33 mV/s. Additionally,
as the intercept in the
cyclic
reversepolarization
and forwardapex current density
polarization was 0.1 mA/cm2. In the forward polarization, passive current
curves.
density and pitting potential were obtained, and the protection potential was defined as the intercept
in the reverse and forward polarization curves.
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2.4.2. AC-Impedance Measurement

2.4.2.AC-Impedance
2.4.2. AC-ImpedanceMeasurement
Measurement
The test specimen was similar to that of the polarization test. Before measuring, passivation was
Thetest
The testspecimen
specimenwaswas similartotothat
thatofofthe
thepolarization
polarizationtest.
test. Beforemeasuring,
measuring,passivation
passivationwaswas
treated at +0 mV (SCE) for 30similar
min. AC impedance was measured atBefore
a passivation potential of between
treated at+0
treated +0mVmV(SCE)
(SCE) for3030min.
min.ACAC impedancewas was measuredatataapassivation
passivationpotential
potentialofofbetween
between
10 kHzat to 0.01 Hz, and for
the AC voltageimpedance
amplitude wasmeasured
10 mV.
10 kHz to 0.01 Hz, and the AC voltage amplitude
10 kHz to 0.01 Hz, and the AC voltage amplitude was 10 mV. was 10 mV.
3. Results
3.3.Results
Results
3.1. The Effect of the Static Load in UNSM Treatment on the Microstructure of Alloy 600
3.1.
3.1.The
TheEffect
Effectofofthe
theStatic
StaticLoad
LoadininUNSM
UNSMTreatment
Treatmentononthe
theMicrostructure
MicrostructureofofAlloy
Alloy600
600
UNSM treatment causes a change in various properties of materials. Figure 2 shows the effect of
UNSM
UNSMtreatment
treatmentcausescausesaachange
change in in various properties of of materials.
materials.Figure
Figure22shows
showsthetheeffect
effectof
the static load in UNSM treatment on the appearance of Alloy 600 through an optical microscope
ofthe
thestatic
staticload
loadininUNSM
UNSMtreatment
treatment on on the appearance of Alloy 600 through an optical microscope
Alloy 600 through an optical microscope
(magnification: ×50). The static load was varied between 10 N, 30 N, and 50 N. The surface
(magnification:×50).
(magnification: ×50).The static
The loadload
static was varied between
was varied 10 N, 3010
between N, N,
and3050 N,
N. The
andsurface
50 N.appearances
The surface
appearances were similar to each other regardless of the static load; many micro valleys were
were similar to each other regardless of the static load; many micro valleys
appearances were similar to each other regardless of the static load; many micro valleys were observed. These valleys
were
observed. These valleys were associated to the applied load and the pitch of UNSM treatment. Figure
were associated
observed. These to valleys
the applied
wereload and the to
associated pitch
theof UNSMload
applied treatment.
and theFigure 3 shows
pitch of UNSM the 3D microscope
treatment. Figure
3 shows the 3D microscope observation. Figure 3 also reveals the effect of the static load in UNSM
observation.
3 shows the 3D Figure 3 also reveals
microscope the effect
observation. of the
Figure static
3 also load the
reveals in UNSM
effect oftreatment
the staticon theinsurface
load UNSM
treatment on the surface topography of Alloy 600 through a 3D microscope (magnification: ×600). An
topography of Alloy 600 through a 3D microscope (magnification: ×600). An
treatment on the surface topography of Alloy 600 through a 3D microscope (magnification: ×600).increase in the static load
An
increase in the static load results in a deeper valley-depth as follows: 9.0 μm for 10 N, 11.1 μm for 30
results in aindeeper
increase the staticvalley-depth
load resultsasinfollows:
a deeper 9.0valley-depth
µm for 10 N, as11.1 µm for
follows: 9.030
μm N,for
and
1011.2
N, 11.1 for 50
µm μm forN30
N, and 11.2 μm for 50 N specimens. It suggested that valley depth may be associated with the intrinsic
specimens.
N, and 11.2Itμm suggested
for 50 Nthat valley depth
specimens. may bethat
It suggested associated with the
valley depth may intrinsic mechanical
be associated properties,
with the intrinsic
mechanical properties, such as yield strength and elastic modulus [21].
such as yield strength and elastic modulus [21].
mechanical properties, such as yield strength and elastic modulus [21].

(a) (b) (c)

(a) (b) (c)
Figure 2. The effect of the static load in UNSM treatment on the appearance of Alloy 600 by optical
Figure2.2.The
Figure Theeffect
effectofofthe
thestatic
staticload
loadininUNSM
UNSMtreatment
treatmenton
onthe
theappearance
appearanceofofAlloy
Alloy600
600by
byoptical
optical
microscope (×50): (a) 10 N; (b) 30 N; (c) 50 N.
microscope(×50):
microscope (×50):(a)
(a)10
10N;
N;(b)
(b)30
30N; N;(c)
(c)50
50N.
N.

(a) (b) (c)

(a) (b) (c)
Figure 3. The
Figure 3. The effect
effectofofthe
thestatic
staticload
loadininUNSM
UNSM treatment onon
treatment thethe
surface topography
surface of Alloy
topography 600 600
of Alloy by 3D
by
Figure 3. The effect of the static load in UNSM treatment on the surface topography of Alloy 600 by
microscope (×600):
3D microscope (a) 10
(×600): (a)N;
10 (b) 30 N;
N; (b) 30 (c)
N; 50
(c)N.
50 N.
3D microscope (×600): (a) 10 N; (b) 30 N; (c) 50 N.
The
The cross-section
cross-section of of the
the microstructure
microstructure by by UNSM
UNSM treatment
treatment waswas observed
observed through
through an an EBSD.
EBSD.
Figure The
4 cross-section
shows the effect of
of the
the microstructure
static load in UNSMby UNSM treatment
treatment on the was observed
grain refinement through
depth an EBSD.
profile of
Figure 4 shows the effect of the static load in UNSM treatment on the grain refinement depth profile
Figure
Alloy 6004 shows
by EBSD.theUntreated
effect of the static load
specimen in UNSM
showed a treatment
typical on the
austenitic grain refinement
microstructure, depth twins
including profile
of Alloy 600 by EBSD. Untreated specimen showed a typical austenitic microstructure, including
of Alloy
and large 600 by(Figure
EBSD.3a). Untreated specimen showed a typical austeniticproceeds
microstructure,
from theincluding
twins andgrains
large grains (Figure Regardless of the static
3a). Regardless of theload, grain
static load,refinement
grain refinement proceeds surface
from the
twins
into the and large
matrix. Ingrains
the (Figure
case of the3a).
10Regardless
N static of
load, the
thestatic
depthload,
of grain
grain refinement
refinement proceeds
was about from
40 µm;the
surface into the matrix. In the case of the 10 N static load, the depth of grain refinement was about 40
surface into
the wasthe matrix. In the casestatic
of the 10 Nandstatic load,90the depth of50grain refinement was aboutin40
μm;depth
the depth 80
was µm 80for
μmthefor30theN30 load,
N static about
load, and about µm for the
90 μm for the N50static load.
N static As
load. shown
As shown
μm;
the the depth
figures below,wasthe80density
μm for of thegrain
30 Nboundary
static load,was and about 90 μm for the 50 N static load. As shown
in the figures below, the density of grain boundary wasincreased
increasedwith
withan anincrease
increaseininthe theUNSM
UNSMstatic
static
in
load the figures below, the density of grain boundary was increased with an increase in the UNSM static
load resulting
resulting inin aa deeper
deeper effective
effective depth.
depth. Figure
Figure 55 summarizes
summarizes the the effect
effect ofof the
the static
static load
load in
in UNSM
UNSM
load resulting
treatment in a deeper effective depth. Figure 5 summarizes the aeffect of the static load in UNSM
treatment on on the
the grain
grain diameter
diameter distribution
distribution of of Alloy
Alloy 600.
600. There
There are
are a lot
lot of
of large
large grain
grain diameters
diameters in in
treatment
the untreated on the grain
specimen. diameter
By distribution
increasing the staticof Alloy
load in 600.
UNSM There are a
treatment, lot of
the large grain
distribution diameters
function ofin
the untreated specimen. By increasing the static load in UNSM treatment, the distribution function
the untreated
smaller grain specimen.
diameter wasByincreased.
increasingNotably,
the static load in UNSM treatment, the distribution function
of smaller grain diameter was increased. Notably,the theUNSM
UNSMtreatment
treatmentcouldcouldrefine
refinethethegrain
grainsize
size in
in
of smaller
addition to grain diameter
increasing the was
static increased.
load, amountNotably,
of the
grain UNSM treatment
refinement, and the could
refined refine
depth. the grain size in
addition to increasing the static load, amount of grain refinement, and the refined depth.
addition to increasing the static load, amount of grain refinement, and the refined depth.
Materials 2019, 12, 3165 5 of 14
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The surface
The
The surface layer
surface layer subjected
layer subjected to
subjected to plastic
to plastic deformation
plastic deformation presents
deformation presents aaa high-density
presents high-density dislocation
high-density dislocation through
dislocation through
through
strikingand
striking
striking andproduces
and producesaaavery
produces verysmall
very small lamellae
smalllamellae deformation-twin
lamellaedeformation-twin
deformation-twin(DT).(DT). However,
(DT).However,
However,due dueto
due toconstant
to constant blows,
constantblows,
blows,
the
the dislocation density
the dislocation density is high,
densityisishigh, creating
high,creating shear
creatingshear bands
shearbands
bands (SB)
(SB) and
(SB) and
and cutting
cutting the
thethe
cutting DT/DTDT/DT
DT/DT intersection.
intersection. The
TheThe
intersection. DT
DT and
DT
anddistort
SB
and SB distort
SB distort the microstructure
the microstructure
the microstructure and changeand into
and change into
grains
change into grains
that that are
are equiaxed
grains that areand
equiaxed
refinedand
equiaxed andthe
by refined by the
development
refined by the
development
of the newly of the
formed newly
grain formed grain
boundaries, boundaries,
thereby reducingthereby
the reducing
grain size the grain
[32–34].
development of the newly formed grain boundaries, thereby reducing the grain size [32–34]. size [32–34].

(a)
(a) (b)
(b) (c)
(c) (d)
(d)
Figure 4.4. The
Figure
Figure Theeffect
effectof
effect ofthe
of thestatic
the static
load
static load
load in UNSM
inin
UNSMUNSM treatment
treatment
treatment on the
on the
on the grain
grain grain refinement
refinement depth
refinement depth profile
profile
depth of
of Alloy
profile of
Alloy 600
600 by600
Alloy EBSD by EBSD
(×600):
by EBSD (×600): (a) untreated;
(a) untreated;
(×600): (b)
(b) 10(b)
(a) untreated; N;1010 N;
(c)N; (c)
30(c) 30
N; 30 N;
(d)N; (d)
50(d) 50 N.
N. 50 N.

(a)
(a) (b)
(b)

(c)
(c) (d)
(d)
Figure5.
Figure
Figure 5.The
5. Theeffect ofthe
effect of
of thestatic
the staticload
static loadin
load inUNSM
in UNSMtreatment
UNSM treatmenton
treatment onthe
on thegrain
the graindiameter
grain diameterdistribution
diameter distributionof
distribution of Alloy
Alloy
600
600 determined
determined from
from the
the EBSD
EBSD area
area of
of Figure
Figure 4:
4: (a)
(a) untreated;
untreated; (b)
(b) 10
10 N;
N; (c)
(c) 30
30 N;
N;
600 determined from the EBSD area of Figure 4: (a) untreated; (b) 10 N; (c) 30 N; (d) 50 N. (d)
(d) 50
50 N.
N.

As described
As described above,
described above, UNSM
above, UNSM treatment
UNSM treatment changed
treatment changed
changed the the microstructure
the microstructure
microstructure fromfrom the
from the surface
the surface into
surface into the
into the
the
As
matrix.
matrix. Figure
Figure 6
6 shows
shows the
the effect
effect of
of the
the static
static load
load in
in UNSM
UNSM treatment
treatment on
on the
the hardness
hardness depth
depth profile
profile
matrix. Figure 6 shows the effect of the static load in UNSM treatment on the hardness depth profile
of Alloy
ofAlloy 600.
Alloy600. The
600.The outermost
Theoutermost surface
outermostsurface revealed
surfacerevealed
revealedthe the maximum
themaximum hardness,
maximumhardness, higher
hardness,higher static
higherstatic load,
staticload, and
load,and higher
andhigher
higher
of
surface hardness.
surfacehardness. The
hardness.The hardness
Thehardness depth
hardnessdepth profiles
depthprofiles reduced
profilesreduced greatly,
reducedgreatly, irrespective
greatly,irrespective
irrespectiveofof the
ofthe static
thestatic load,
staticload, and
load,and the
andthe
the
surface
hardness-depth
hardness-depth relationship
relationship showed
showed aa polynomial
polynomial expression.
expression. Although
Although aa higher
higher static
static load
load resulted
resulted
hardness-depth relationship showed a polynomial expression. Although a higher static load resulted
inaalittle
in littlehigher
higherof
ofaahardness
hardnessdepth
depthprofile,
profile,similar
similarhardness
hardnessattenuation
attenuationwaswasrevealed
revealedas asfollows;
follows;yy
means the hardness (HV) and x implies the depth (μm) from top surface. As
means the hardness (HV) and x implies the depth (μm) from top surface. As shown in below, the shown in below, the
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in a little higher of a hardness depth profile, similar hardness attenuation was revealed as follows;
Materials 2019, 12, x FOR PEER REVIEW 6 of 14
y means
surface the hardness
hardness (HV)
increases and
with anxincrease
impliesin
the
thedepth
static (µm) from top surface.
load. However, As shown
the hardness in below,
depth profile of
the surface
higher
surface hardness
static
hardness increases
load increases
specimen withwith
decreasesan more
increase
an increase in the
compared
in the static
staticto load.
that
load. of However,thethe
lower static
However, hardness
load depth
specimen.
hardness depth profile
Finally,
profile of
of
thehigher
effect static
of the load specimen
static load on decreases
hardness more
depth compared
profile to that
diminished of lower
from thestatic
depthload
of
higher static load specimen decreases more compared to that of lower static load specimen. Finally,specimen.
about 500 Finally,
μm.
the effect
the effect of
of the
the static
static load
load on
on hardness
hardness depth
depth profile
profile diminished
diminished from
from the
thedepth
depthofofabout
about500
500µm.
μm.

Figure 6. The effect of the static load in UNSM treatment on the hardness depth profile of Alloy 600.
Figure 6. The effect of the static load in UNSM treatment on the hardness depth profile of Alloy 600.
Figure 6. The effect of the static load in UNSM treatment on the hardness depth profile of Alloy 600.
Figure
Figure 77 shows
shows the
the effect
effect of
of the
the static
static load
load in
inUNSM
UNSMtreatment
treatment on on the
thedislocation
dislocation density
density of
ofAlloy
Alloy
600 through
600 through kernel
Figure 7kernel average
showsaverage
the effect misorientation
of the static load
misorientation (KAM).
in UNSM
(KAM). Dislocation
treatment
Dislocation densities
on the
densities can be obtained
dislocation
can be obtaineddensity using
usingof a
a Alloy
KAM
KAM
600 map.
map.through In the KAM
kernelmap,
In the KAM map,
average
the red the red > yellow
> yellow > green
misorientation >
(KAM). green color
Dislocation
color series suggests
densities
series suggests a higher dislocation
can bedislocation
a higher obtained using a
density
density
KAM map. qualitatively.
qualitatively.InAs
theshown
KAMAs in
shown
map,
Figure in 6,
the Figure
red 6, an increase
an >increase
yellow > green
in incolor
the
the static static
series
load, load, increased
suggests
increased the dislocation
thea dislocation
higher dislocation
density
density
density
resultingresulting in anAs
qualitatively.
in an increasedincreased
shown in
depth. depth.
Figure 6, an increase in the static load, increased the dislocation
density resulting in an increased depth.

(a) (b) (c) (d)

Figure 7.
Figure (a)effect
The
7. The effect of the static load(b)
in UNSM
UNSM treatment on (c)
treatment on the dislocation
the dislocation density (d)
density of
of Alloy 600
Alloy 600 by
by
kernel average
kernel
Figure average misorientation;
misorientation;
7. The effect (a)load
(a)
of the static untreated;
in UNSM(b) treatment
10 N; (c) 30onN;the
(d)dislocation
50 N. density of Alloy 600 by
kernel average misorientation; (a) untreated; (b) 10 N; (c) 30 N; (d) 50 N.
However, ititisisinteresting
However, interestingthatthatthethe
depth
depthof grain refinement
of grain refinement is different to theto
is different hardness depth profile,
the hardness depth
as the depth
profile, of high
as the depth
However, dislocation density
of high dislocation
it is interesting is
that the depthdifferent
density with the
is different
of grain hardness
refinement depth
with isthe profile.
hardness
different This
depth
to the difference
profile.depth
hardness can
This
be explained
difference
profile, as can as
the be follows;
explained
depth a sharp
of high increase
asdislocation
follows; a sharpin the hardness
increase
density of the
in the with
is different outer
hardness surface was
of the outer
the hardness as a result
surface
depth of grain
was This
profile. as a
refinement
result and the increased dislocation density, as shown in Figures 5 and
difference can be explained as follows; a sharp increase in the hardness of the outer surface was 7as
of grain refinement and the increased dislocation density, as shown 7
in (it is
Figure noteworthy
5 and that
Figure the
(ita
detection
is noteworthy
result depth
of grain that by EBSD was
the detection
refinement about
and thedepth 120 µm).
by EBSD
increased The grain
was about
dislocation refinement
120 as
density, μm). through
shownThe in
grainUNSM
Figure treatment
refinement
5 and Figure was
through
7 (it
limited
UNSM to the
treatment outer
was surface,
limited but
to the
the increased
outer hardened
surface, but the depth
increased was deeper
hardened
is noteworthy that the detection depth by EBSD was about 120 μm). The grain refinement through than
depth the
was depth
deeperof grain
than
refinement
the
UNSMdepth ofvia
treatment a work
grain was hardening
refinement
limited to mechanism.
viathe
a work
outerhardening
surface, but mechanism.
the increased hardened depth was deeper than
Since
Since of
the depth UNSM
UNSM treatment
graintreatment involves
refinementinvolves
via a work hitting
hitting the surface
the surface
hardening numerous times
numerous
mechanism. times using
using aa strong
strong WC WC tiptip in
in aa
very short
very short period,
Since period, high
UNSM high energy
energy
treatment can be
can
involves be applied
appliedthe
hitting tothe
to the surface
surface
surface ofmaterials,
of
numerous materials, leading
timesleading
using ato toaatransformation.
transformation.
strong WC tip in a
Figure 8 shows
very short thehigh
period, effect of the
energy static
can load intoUNSM
be applied treatment
the surface on the XRD
of materials, patterns
leading of Alloy 600.
to a transformation.
Phase
Figuretransformation wereofnot
8 shows the effect thedetected in XRD
static load analysis,
in UNSM but an increase
treatment in thepatterns
on the XRD static load increased
of Alloy 600.
Phase transformation were not detected in XRD analysis, but an increase in the static load increased
Materials 2019, 12, 3165 7 of 14
Materials 2019, 12, x FOR PEER REVIEW 7 of 14

Materials
the half82019,
Figure 12, xof
shows
width FOR
the PEERThe
effect
peak. REVIEW
of increased
the static half
loadwidth
in UNSMof thetreatment on thethe
peak suggests XRD 7 of
patternsofofamorphous
formation Alloy 14
600.
Phase transformation were not detected in XRD analysis, but an increase in the static load
state [35], and it is considered that this may be related to the grain refinement using UNSM treatment. increased
the half
the half width
width of of peak.
peak. The
The increased
increased half
half width
width ofof the
the peak
peak suggests
suggests the
the formation
formation of of amorphous
amorphous
state [35], and it is considered that this may be related to the grain refinement using UNSM treatment.
state [35], and it is considered that this may be related to the grain refinement using UNSM treatment.

(a) (b)
Figure 8. The effect of the (a) static load in UNSM treatment on the XRD (b)
patterns of Alloy 600: (a) 20°–
80°; (b) 42°–45°.
Figure 8.
Figure 8. The
The effect
effectofofthe
thestatic
staticload
loadinin UNSM
UNSM treatment
treatment onon
thethe
XRDXRD patterns
patterns of Alloy
of Alloy 600:600: (a)◦ –80
(a) 20 ◦;
20°–
(b) ◦ ◦
80°;42
3.2. The (b)–45 of. the Static Load in UNSM Treatment on the Residual Stress of Alloy 600.
42°–45°.
Effect
3.2. The Effectconfirmed
It was of the Static LoadUNSMin UNSM Treatmentresulted
on the Residual Stress of Alloy 600.
3.2. The Effect of the Staticthat
Load in UNSM treatment in grain
Treatment on the Residual refinement,
Stress the formation of an
of Alloy 600.
amorphous solid, increased dislocation density, and high hardness. To understand
It was confirmed that UNSM treatment resulted in grain refinement, the formation of an amorphous how these
It was
microstructural confirmed that
properties affectUNSM treatment
theandresidual resulted in grain refinement, the formation of ana
solid, increased dislocation density, high stress, the residual
hardness. stresseshow
To understand were determined
these using
microstructural
amorphous
nanoindentation solid,technique
increased dislocation density, andeffect
highofhardness. To understand how these
properties affect the residual[36,37].
stress,Figure 9 shows
the residual the
stresses the static load
were determined in UNSM
using treatment
a nanoindentation on
microstructural
the representative properties affect
load-displacement the residual
curves stress,
of the
Alloy residual
600 stresses
using were determined
Nano-indentation. using a
Untreated
technique [36,37].technique
nanoindentation Figure 9 shows
[36,37].theFigure
effect 9ofshows
the static load
effectinofUNSM
theUNSM-treated treatment
the static load in on the representative
UNSM treatment on
specimen suggests
load-displacement that
curvesthe stress-free-state
of Alloy 600 using curves of
Nano-indentation. specimen
Untreated were located
specimen suggests more left
that the
the representative
than those of thecurves load-displacement
treated stress-free curves
state, specimenof Alloy
which demonstrates 600 using
themore Nano-indentation.
presence of compressive Untreated
residual
stress-free-state
specimen suggests that of
the UNSM-treated
stress-free-state curves ofwere located
UNSM-treated left than
specimen those
were of themore
located treated
left
stress [38].
stress-free Regardless
state, which of the static
demonstrates load,
the the
presence compressive
of compressiveresidual stress
residual was
stress higher
[38]. at the
Regardless outer
of the
than those
surface, of the treated
as shown stress-free
in figures below. state, which demonstrates the presence of compressive residual
static
stressload,
[38]. the compressive
Regardless of theresidual
static stress
load, was higher at the outer
the compressive surface,
residual stressaswas
shown in figures
higher at thebelow.
outer
surface, as shown in figures below.

(a) (b) (c)

Figure 9.
Figure 9. The effect of
(a)effect of the
the static
static load
load in
in UNSM
UNSM treatment
treatment on
(b) on thetherepresentative
representative load-displacement
load-displacement
(c)
curves
curves of
of Alloy
Alloy 600
600 by
by nano-indentation:
nano-indentation: (a) (a) 10
10 N;
N; (b)
(b) 30
30 N;
N; (c)
(c) 50
50 N.
N.
Figure 9. The effect of the static load in UNSM treatment on the representative load-displacement
The
The residual
curves of Alloystress
residual 600 bycalculated
stress from
fromFigures
nano-indentation:
calculated 99 (b)
(a) 10 N;
Figure and
and3010N;summarized
(c) 50
Figure the effect
10N.summarized theofeffect
the static load
of the in
static
UNSM
load in treatment on the residual
UNSM treatment stress depth
on the residual stressprofile
depth of Alloyof600.
profile High
Alloy 600.compressive residual
High compressive stress
residual
was The residual
obtained stress
through an calculated
increase infrom
the Figure
static 9
loadand
and Figure
the 10
stress summarized
was reduced the
witheffect
depth,
stress was obtained through an increase in the static load and the stress was reduced with depth, of the
as static
shown as
load
in in
Figure
shown UNSM
in10. treatment
Figure 10. on the residual stress depth profile of Alloy 600. High compressive residual
stressFormation
was obtained through
of the an increase
compressive in thestress
residual staticthrough
load andUNSM
the stress was reduced
treatment can bewith depth, as
explained as
shown inthe
follows: Figure 10. of the surface the material was from cyclic plastic loading, due to progressive
peening
peening effects. Outer layers experience an in-plane stretching plastic deformation, whereas the elastic
sub-surface attempts to maintain its original shape, hence generating compressive residual stress
at the surface [39,40]. Additionally, a small portion of the applied stress is stored in the form of
residual stresses within the structure as a tangled network of dislocations [41]. A very fine grain with
Materials 2019, 12, 3165 8 of 14

high dislocation density as a result of UNSM treatment could facilitate the formation of compressive
Materials 2019, 12, x FOR PEER REVIEW 8 of 14
residual stress.

Figure 10. The effect of the static load in UNSM treatment on the residual stress depth profile of Alloy
600.

Formation of the compressive residual stress through UNSM treatment can be explained as
follows: the peening of the surface the material was from cyclic plastic loading, due to progressive
peening effects. Outer layers experience an in-plane stretching plastic deformation, whereas the
elastic sub-surface attempts to maintain its original shape, hence generating compressive residual
stress at the surface [39,40]. Additionally, a small portion of the applied stress is stored in the form of
residual stresses within the structure as a tangled network of dislocations [41]. A very fine grain with
high Figure
dislocation
Figure 10.
density
The
10. The effectofas
effect
athe
ofthe result
static
static
ofload
load
UNSM treatment
in UNSM
in UNSM
could
treatment
treatment onfacilitate
on the
the formation
the residual
residual stressstress
ofprofile
depthdepth
profile
compressive
of
of Alloy
residual
600. stress.
Alloy 600.

3.3. The Effect

3.3. The Effect of
of the
the Static
Static Load
Load inin UNSM
UNSM Treatment
Treatment on Corrosion
onthrough
CorrosionUNSMProperties
Properties
Formation of the compressive residual stress treatment can be explained as
Figure
Figure 11 shows the effect of the static load in UNSM treatmentthe
follows: the 11 shows
peening the
of effect
the of
surface the static
the load
material in wasUNSMfrom treatment
cyclic on
plastic on polarization
loading, due to
the polarizationcurve of Alloy
progressive
curve of
600 in a deaerated solution of 1% NaCl at 30 ◦ C. Regardless of the static load, the specimens display the
peening
Alloy 600effects. Outer layers
in a deaerated solutionexperience
of 1% NaCl an in-plane
at 30 °C.stretching
Regardlessplastic
of the deformation,
static load, the whereas
specimens the
trans-passive
elastic sub-surface
display transition.
the trans-passive Table
attempts to3 summarizes
maintain
transition. its the
Table 3 corrosion
original shape,
summarizes factors
the(Ecorrosion
hence : pitting
generating
pitting potential,
(EpittingE:protection
compressive
factors pitting:
residual
protection
stress at the
potential, Epotential,
surface
protection
and ipassive
[39,40].
: protection : passiveand
Additionally,
potential, current
a small :density)
passiveofobtained
ipassiveportion from
the applied
current Figure
stress
density) 11 due
is stored
obtained intothe
from the static
form
Figure of
11
load
due in
residual UNSM
to thestresses treatment.
static within
load inthe Regardless
structure
UNSM of the static
as a tangled
treatment. load
network
Regardless value, the pitting
of dislocations
of the potential
[41]. Athe
static load value, was
very increased,
fine grain
pitting and
with
potential
the
high passive current
dislocation density
density as was
a decreased
result of UNSM compared
treatment to the
coulduntreated
facilitate
was increased, and the passive current density was decreased compared to the untreated specimen, specimen,
the but
formation the
of higher
compressivestatic
load decreased
residual
but the the protection
stress.static
higher potential.
load decreased This behavior
the protection implies
potential. thatbehavior
This the staticimplies
load enhances resistance
that the static load
to
enhances resistance to corrosion through UNSM treatment, as indicated by the critical value.than
corrosion through UNSM treatment, as indicated by the critical value. A static load greater the
A static
critical
3.3. The
load value
greater may
Effectthan be
of thethe harmful
Static to
in corrosion
Loadvalue
critical UNSM
may be resistance.
Treatment
harmfulon toCorrosion
corrosionProperties
resistance.
Figure 11 shows the effect of the static load in UNSM treatment on the polarization curve of
Alloy 600 in a deaerated solution of 1% NaCl at 30 °C. Regardless of the static load, the specimens
display the trans-passive transition. Table 3 summarizes the corrosion factors (Epitting: pitting
potential, Eprotection: protection potential, and ipassive: passive current density) obtained from Figure 11
due to the static load in UNSM treatment. Regardless of the static load value, the pitting potential
was increased, and the passive current density was decreased compared to the untreated specimen,
but the higher static load decreased the protection potential. This behavior implies that the static load
enhances resistance to corrosion through UNSM treatment, as indicated by the critical value. A static
load greater than the critical value may be harmful to corrosion resistance.

Figure 11. The effect of the static load in UNSM treatment on the polarization curve of Alloy 600 in
Figure 11. 1%
deaerated TheNaCl
effectatof
30the
◦ C.static load in UNSM treatment on the polarization curve of Alloy 600 in
deaerated 1% NaCl at 30 °C.
Table 3. Corrosion factors obtained from Figure 10 by the static load in UNSM treatment.
Table 3. Corrosion factors obtained from Figure 10 by the static load in UNSM treatment.
Static Load Untreated 10 N 30 N 50 N
Static
Epitting Load
, V(SCE) Untreated
0.218 0.306 10 N0.31330 N 0.345
50 N
E , V(SCE)
Eprotection , V(SCE)
pitting 0.146 0.218 0.221 0.306 0.313
0.198 0.345
0.079
ipassive , A/cm2 at 0
10-6.074 10-6.819 10-6.658 10-6.593
V(SCE)

Figure 12
Figure 11.shows
The effect
the of the of
effect static
theload
staticinload
UNSM treatment
in UNSM on the polarization
treatment curve of Alloy
on the AC impedance 600 in
measurement
deaerated
for the passive1% NaCl
film at 30 °C.
formed at 0 V (SCE) in a deaerated solution of 1% NaCl at 30 ◦ C. Figure 12a

Table 3. Corrosion factors obtained from Figure 10 by the static load in UNSM treatment.

Static Load Untreated 10 N 30 N 50 N

Epitting, V(SCE) 0.218 0.306 0.313 0.345
 Materials 2019, 12, x FOR PEER REVIEW 9 of 14

Eprotection, V(SCE) 0.146 0.221 0.198 0.079

ipassive, A/cm2 at 0 V(SCE) 10-6.074 10-6.819 10-6.658 10-6.593
Materials 2019, 12, 3165 9 of 14
Figure 12 shows the effect of the static load in UNSM treatment on the AC impedance
measurement for the passive film formed at 0 V (SCE) in a deaerated solution of 1% NaCl at 30 °C.
represents
Figure 12athe Nyquist plot,
represents and Figure
the Nyquist plot,12band
plotted the12b
Figure polarization resistance
plotted the obtained
polarization from Figure
resistance 12a
obtained
using Randel’s model. UNSM treatment enhanced the polarization resistance regardless
from Figure 12a using Randel’s model. UNSM treatment enhanced the polarization resistance of the static
loading, until
regardless of the
the critical value where
static loading, until the
the resistance started
critical value to decrease.
where This behavior
the resistance started towas similarThis
decrease. to
the polarization test results.
behavior was similar to the polarization test results.

(a) (b)
Figure12.
Figure 12.The
Theeffect
effectofofthe
thestatic
staticload
loadin
inUNSM
UNSMtreatment
treatmentononthe
theAC
ACimpedance
impedancemeasurement
measurementforforthe
the
passivefilm
passive film formed
formed at 0atV0(saturation
V (saturation
camelcamel electrode,
electrode, SCE)
SCE) in in deaerated
deaerated 1% NaCl1% ◦
at NaCl
30 C:at
(a)30 °C: (a)
Nyquist
Nyquist
plot plot
and (b) and (b) polarization
polarization resistance.resistance.

4.4.Discussion
Discussion
As
As described
described above, above, UNSM UNSM treatment
treatment of of Alloy
Alloy 600 600 changed
changed its its mechanical
mechanical properties,
properties,
microstructural properties, and corrosion resistance, increasing the
microstructural properties, and corrosion resistance, increasing the static load. Surface hardness static load. Surface hardnesswas
was greatly
greatly increased,
increased, and and the hardness
the hardness depthdepth
profileprofile was reduced
was reduced from the from the surface
surface to the matrix.
to the matrix. UNSM
UNSM
treatmenttreatment could the
could refine refine thesize,
grain grain size,
and and moreover,
moreover, the higher
the higher the static theload,
static theload, the greater
greater the amountthe
amount of grain refinement and the refined depth were increased. When
of grain refinement and the refined depth were increased. When the static load increases, high the static load increases, high
compressive
compressiveresidual
residualstress
stressisiscaused,
caused,and andthe
thestress
stressreduces
reduceswith withdepth.
depth.Regardless
Regardlessof ofthe
thestatic
staticload,
load,
UNSM
UNSM treatment enhanced the resistance to corrosion, but decreased when the load exceededthe
treatment enhanced the resistance to corrosion, but decreased when the load exceeded the
critical value. Why did the static load in UNSM treatment enhance the
critical value. Why did the static load in UNSM treatment enhance the corrosion resistance? Why was corrosion resistance? Why was
its
itseffect
effectdependent
dependentupon uponthe thestatic
staticloadloadvalues?
values?
Figure 13 illustrates the effect of
Figure 13 illustrates the effect of the staticthe static load under
load theundercritical
the UNSM
criticalcondition
UNSM conditionon the corrosion
on the
factors
corrosionof Alloy
factors 600. Specifically,
of Alloy under the critical
600. Specifically, under the static load, static
critical increasing
load, the static load
increasing the improved
static load
the pitting potential
improved the pitting and protection
potential andpotential,
protectionand it reduced
potential, andtheitpassive
reducedcurrent density
the passive compared
current to
density
untreated specimen.
compared to untreated specimen.
This
Thisstudy
studysought
soughttotounderstand
understandthe theenhancement
enhancementof ofcorrosion
corrosionresistance
resistancein inregard
regardtotograin
grain
refinement
refinement and residual stress. Corrosion behavior through the reduction of grain sizeisisdependent
and residual stress. Corrosion behavior through the reduction of grain size dependent
on
onthe
thealloy
alloytype,
type,corrosion
corrosionenvironment,
environment,and andcorrosion
corrosionforms forms[42].
[42].Claims
Claimsthat thatimproved
improvedcorrosion
corrosion
resistance is as a result of grain refinement are generally attributed to
resistance is as a result of grain refinement are generally attributed to an improved passive an improved passive filmfilm
[43–46].
[43–
Grain boundaries contain higher energies than the bulk, and as such
46]. Grain boundaries contain higher energies than the bulk, and as such [47] are more chemically [47] are more chemically active,
hence
active,a high
hencedensity
a high of grain of
density boundaries increasesincreases
grain boundaries the reactivity at the surface
the reactivity at thedue to increased
surface electron
due to increased
activity and diffusion. In addition to enhanced rates of diffusion, the
electron activity and diffusion. In addition to enhanced rates of diffusion, the main consequence main consequence of sites suchof
as grain boundaries and triple junctions, include reduced atom coordination
sites such as grain boundaries and triple junctions, include reduced atom coordination and increased and increased electron
activity
electron[48]. Increased
activity reactivity,reactivity,
[48]. Increased coupled with coupledmore sites
with for the
more sitesnucleation of an oxide
for the nucleation of anfilm on the
oxide film
surface of grain-refined materials is suggested, to result in a more
on the surface of grain-refined materials is suggested, to result in a more rapid formation of a rapid formation of a protective
layer. In thelayer.
protective case ofInaustenitic
the case of stainless
austeniticsteels and Ni-alloys,
stainless steels andit was reportedit that
Ni-alloys, wasNano-crystallization
reported that Nano-
improved the corrosion resistance [45,49–52].
crystallization improved the corrosion resistance [45,49–52].
Figure 14 shows the effect of the static load in UNSM treatment on lattice plane spacing of Alloy
600. Figure 14a shows the lattice plane spacing via the static load where an increase in the load reduced
the lattice plane spacing. From this result, the decrement model of lattice plane spacing using UNSM
treatment was suggested as shown in Figure 14b, and the driving force for the decrement model is the
compressive residual stress induced through UNSM treatment.
 Materials 2019, 12, 3165 10 of 14
Materials 2019, 12, x FOR PEER REVIEW 10 of 14

Figure 13. The effect of the static load under the critical UNSM condition on the corrosion factors of
Alloy 600.

Figure 14 shows the effect of the static load in UNSM treatment on lattice plane spacing of Alloy
600. Figure 14a shows the lattice plane spacing via the static load where an increase in the load
reduced the lattice plane spacing. From this result, the decrement model of lattice plane spacing using
UNSM treatment
Figure
Figure 13.13. was
TheThe
effect suggested
effect
of of the
the static asload
static
load shown
under in the
under
the Figure 14b,
critical
critical and
UNSM
UNSM the driving
condition
condition on on force
thethe for factors
thefactors
corrosion
corrosion decrement
of of
model is the
Alloy compressive
600.
Alloy 600. residual stress induced through UNSM treatment.

Figure 14 shows the effect of the static load in UNSM treatment on lattice plane spacing of Alloy
600. Figure 14a shows the lattice plane spacing via the static load where an increase in the load
reduced the lattice plane spacing. From this result, the decrement model of lattice plane spacing using
UNSM treatment was suggested as shown in Figure 14b, and the driving force for the decrement
model is the compressive residual stress induced through UNSM treatment.

(a) (b)
Figure
Figure14.
14.TheTheeffect of of
effect thethe
static load
static in UNSM
load treatment
in UNSM on lattice
treatment plane
on lattice spacing
plane of Alloy
spacing 600; (a)
of Alloy 600;
measured lattice
(a) measured plane
lattice spacing
plane andand
spacing (b) (b)
decrement model
decrement of lattice
model plane
of lattice spacing
plane byby
spacing UNSM
UNSM treatment.
treatment.

Basedon
Based onthetheresults
resultsofofO. O.Takakuwa
Takakuwa[53], [53],corrosion
corrosionresistance
resistanceisisimproved
improvedwhen whencompressive
compressive
residual stress is induced through cavitation peening; this might
residual stress is induced through cavitation peening; this might be the reason why the reduction be the reason why the reductionofof
inter-atomic spacing due
inter-atomic (a)
duetoto thethecompressive
compressive stressstress
at the at surface
the facilitates (b)
the growththe
surface facilitates andgrowth
maintenance
and
of Figure
the passivation
maintenance film. The compressive residual stress enhances not only
14. The effect of the static load in UNSM treatment on lattice plane spacing of Alloy 600; (a) the
of the passivation film. The compressive residual stress the mechanical
enhances not properties,
only
but also
mechanical the corrosion
measuredproperties,
lattice planeresistance.
but alsoand
spacing theTherefore,
corrosion
(b) decrement it resistance.
can be concluded
model Therefore,
of lattice that spacing
plane UNSM
it can be treatment
by concluded refines
that the
UNSM treatment. UNSMgrain
size and this
treatment facilitates
refines the grain
the grain sizeboundary
and thisdiffusion,
facilitatesthereby
the strengthening
grain boundary the diffusion,
passive film, and its
thereby
treatment
strengthening induces
Based on the compressive
theresults
passiveoffilm, residual stress
and its treatment
O. Takakuwa which facilitates
induces compressive
[53], corrosion the surface
resistance is residual diffusion,
improved stress
whenand
which subsequently
facilitates
compressive
improves
the surface
residual the
stress ispassivation
diffusion,
induced of Alloy
andthrough
subsequently 600. improves
cavitation peening; thethis
passivation
might beofthe Alloy
reason600.why the reduction of
However,
However,
inter-atomic aa static
spacing load
dueloadtoexceeding
exceeding the
the compressive thecritical
criticalvalue
stressvaluecanthe
at degrade
can degrade
surface thefacilitates
corrosion resistance,
the corrosion as shown
resistance,
the growth andas
in Figure 15.
shown in Figure
maintenance Figure
of the 15
15. Figure illustrates
15 illustrates
passivation the
film. The effect of
the effect the static
of the static
compressive load in the critical
load instress
residual UNSM
the critical
enhancesUNSM condition
notconditionon
only the the
on
corrosion
the corrosion
mechanical factors
properties, of Alloy
factors of
but 600.
also Through
Alloy 600. Through
the corrosionincreasing the static
increasing
resistance. theload,
staticthe
Therefore, itprotection
load,
canthe potentialpotential
beprotection
concluded was decreased
that UNSM was
as the passive
decreased
treatment as thecurrent
refines passive density
the grain current increased,
size density
and this although
increased,
facilitatesthe pitting
although
the grain potential
the pitting was
boundary increased.
potential was Specifically,
diffusion, increased.
thereby
the reduction
Specifically,
strengthening the
theofpassive
corrosion
reduction film,resistance
of corrosion
and through UNSM
resistance
its treatment treatment
through
induces UNSM
compressive maytreatment
be as a result
residual mayof
stress beanother
which factor.
as facilitates
a result of
another
the Figure
surfacefactor.16 illustrates
diffusion, the effect ofimproves
and subsequently the staticthe load on the surface
passivation of Alloymorphologies
600. and mechanical
overlapping
However, via UNSM
a static loadtreatment.
exceedingAs theshown
critical in value
the optical micrographs,
can degrade UNSM treatment
the corrosion resistance,ledas to
valley
shown inpitch
Figure by15.pitch, and15many
Figure lines, the
illustrates likeeffect
cracks, ofwere also load
the static observed.
in theMechanically
critical UNSMoverlapped
condition on lines
thewere observed
corrosion in SEM
factors images.
of Alloy 600.B.Through
Wu [54] reported
increasing thatthethe surface
static load,canthe
beprotection
damaged by increasing
potential wasthe
friction between
decreased the striking
as the passive current tip density
and surface due to high
increased, althoughstaticthe
load duringpotential
pitting UNSM process.
was increased.
Specifically, the reduction of corrosion resistance through UNSM treatment may be as a result of
another factor.
terials 2019, 12, x FOR PEER REVIEW 12 of 15
Materials 2019, 12, 3165 11 of 14
Materials 2019, 12, x FOR PEER REVIEW 11 of 15

Figure 15. The effect of the static load over the critical UNSM condition on the corrosion factors of
Alloy 600.

Figure 16 illustrates the effect of the static load on the surface morphologies and mechanical
overlapping via UNSM treatment. As shown in the optical micrographs, UNSM treatment led to
valley pitch by pitch, and many lines, like cracks, were also observed. Mechanically overlapped lines
Figure
wereFigure 15. The
observed effect of the static
in SEM load overreported
the critical UNSM condition onbe
the corrosion by
factors of
15. The effect images. B. Wu
of the static load[54] that
over the critical the surface
UNSM conditioncan
on thedamaged increasing
corrosion factors of
Alloy 600.
the friction between the striking tip and surface due to high static load during UNSM process.
Alloy 600.

Static
Figure 16 illustrates the10 N of the static load30onNthe surface morphologies
effect 50 N and mechanical
load
overlapping via UNSM treatment. As shown in the optical micrographs, UNSM treatment led to
valley pitch by pitch, and many lines, like cracks, were also observed. Mechanically overlapped lines
were observed OMin SEM images. B. Wu [54] reported that the surface can be damaged by increasing
the friction between
(×600) the striking tip and surface due to high static load during UNSM process.

Static
10 N 30 N 50 N
load

SEM
OM
(×1500)
(×600)

the static
Figure 16. The effect of the static load
load on
on the
the surface
surface morphologies
morphologies and mechanical
mechanical overlapping by
UNSM treatment.
SEM
(×1500)
From
From the
theOMOMandandSEM
SEMobservations,
observations, thethe
mechanical
mechanicaloverlapping
overlapping model of UNSM
model of UNSMtreatment was
treatment
proposed as shown Figure 17; in the initial stage (Figure 17a), WC tip strikes the surface.
was proposed as shown Figure 17; in the initial stage (Figure 17a), WC tip strikes the surface. When When the tip
travels
the tipalong thealong
travels movingthedirection,
movingmany wavesmany
direction, are formed
waves(Figure 17b). Through
are formed (Figurethe repeated
17b). process,
Through the
the overlapped
repeated area,
process, the which acts asarea,
overlapped the initiate
which actssite as
of the
corrosion,
initiate could
site ofbe formed. could
corrosion, This overlapped
be formed.
Figure 16. The effect of the static load on the surface morphologies and mechanical overlapping by
wave formation may
This overlapped wavereduce the corrosion
formation may reduce resistance; and increasing
the corrosion resistance;theandstatic load could
increasing accelerate
the static load
UNSM treatment.
corrosion and decrease
could accelerate the and
corrosion protection
decreasepotential.
the protection potential.
From the OM and SEM observations,
Materials 2019,the
12, xmechanical overlapping model of UNSM treatment
FOR PEER REVIEW
was proposed as shown Figure 17; in the initial stage (Figure 17a), WC tip strikes the surface. When
the tip travels along the moving direction, many waves are formed (Figure 17b). Through the
repeated process, the overlapped area, which acts as the initiate site of corrosion, could be formed.
This overlapped wave formation may reduce the corrosion resistance; and increasing the static load
could accelerate corrosion and decrease the protection potential.
(a) (b) (c) (d)
Figure
Figure 17. Mechanical overlapping model by17.
UNSMMechanical
treatment:overlapping
(a) beginningmodel
stage; by UNSM
(b) wave treatment: (a) beginning stage
formation;
formation;
(c) ultrasonic tip movement; (d) overlapped (c)formation
area ultrasonicand
tip the
movement; (d) overlapped
evidentiary image. area formation and the evidentiary

5. Conclusions
This work was centered on the effect of the static load in UNSM treatment on
properties. The conclusions are as follows:
(1) Regardless of the magnitude of the static load, UNSM treatment enhanced
Materials 2019, 12, 3165 12 of 14

5. Conclusions
This work was centered on the effect of the static load in UNSM treatment on the corrosion
properties. The conclusions are as follows:
(1) Regardless of the magnitude of the static load, UNSM treatment enhanced the corrosion
resistance, until it decreased when the load exceeded the critical value. Increasing the static load under
the critical static load enhanced the pitting potential and protection potential, and reduced the passive
current density compared to untreated samples. It can be concluded that UNSM treatment can refine
the grain size which facilitates the grain boundary diffusion, and therefore, strengthen the passive film;
and its treatment could induce the compressive residual stress, which enhances the surface diffusion
and subsequently improves the passivation of Alloy 600.
(2) However, a high static load exceeding the critical value can degrade the corrosion resistance.
After increasing the static load, the protection potential was reduced and the passive current density
was increased. The surface may be damaged by increasing the friction between the strike tip and surface
due to the high static load during the UNSM process. Through that repeated process, an overlapped
wave, which acts as the initiating site of corrosion, may be formed. This overlapped wave formation
may reduce the corrosion resistance.

Author Contributions: K.T.K. and Y.S.K. conceived and designed the experiments, analyzed the data, and wrote
the paper.
Funding: This research received no external funding
Acknowledgments: UNSM treatment was carried out with the help of Designmecha Co.; Pyoun, Y.S.;
and Amanova, A. from Sunmoon University. We appreciate their help.
Conflicts of Interest: The authors declare no conflict of interest.

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