energies

Article
Study of Material Compatibility for a Thermal Energy
Storage System with Phase Change Material
Songgang Qiu 1, * ID
, Laura Solomon 1 ID
and Ming Fang 2
1 Department of Mechanical and Aerospace Engineering, Benjamin M. Statler College of Engineering and
Mineral Resources, West Virginia University, Morgantown, WV 26506, USA; laura.solomon@mail.wvu.edu
2 Bechtel National Incorporation, Hanford Waste Treatment Plant, Richland, WA 99354, USA;
mfang@bechtel.com
* Correspondence: songgang.qiu@mail.wvu.edu; Tel.: +1-304-293-3342

Received: 21 February 2018; Accepted: 5 March 2018; Published: 6 March 2018

Abstract: The suitability of stainless steel 316L and Inconel 625 for use in a latent heat thermal energy
storage (TES) system was investigated. A NaCl–NaF eutectic mixture with a melting temperature of
680 ◦ C was used as the phase change material (PCM). Containers were filled with the PCM prior to
heating to 750 ◦ C, then examined after 100 and 2500 h of high-temperature exposure by analyzing the
material surface and cross-section areas. A small amount of corrosion was present in both samples
after 100 h. Neither sample suffered significant damage after 2500 h. The undesirable inter-granular
grain boundary attack found in SS316L samples was in the order of 1–2 µm in depth. On Inconel
625 sample surface, an oxide complex formed, resisting material dissolution into the PCM. The surface
morphology of tested samples remained largely unchanged after 2500 h, but the corrosion pattern
changed from an initially localized corrosion penetration to a more uniform type. After 2500 h,
the corrosion depth of Inconel 625 remained at roughly 1–2 µm, indicating that the corrosion rate
decelerated. Both materials demonstrated good compatibility with the chosen NaF–NaCl eutectic
salt, but the low corrosion activity in Inconel 625 samples shows a performance advantage for long
term operation.

Keywords: thermal energy storage (TES); phase change material (PCM); concentrating solar power (CSP);
molten salt; material compatibility; corrosion rate

1. Introduction
One of the main challenges limiting the widespread implementation of solar and wind energies
for grid-scale electricity generation is the transient nature of the renewable energy resources.
One promising technology is solar thermal power generation because surplus solar radiation can be
stored directly as thermal energy without costly conversion losses. Thermal energy storage (TES) has
been implemented at operational concentrating solar power (CSP) plants using the sensible heat of
a large amount of molten salt [1–3]. These systems require complex pumping systems, large storage
mass volumes for megawatt power generation, a high degree of insulation to prevent the molten salt
from solidifying, and they have a low solar to electric efficiency of only 15 to 20 percent. A latent
heat-based TES system vastly reduces the overall size and thus the cost of storage systems by utilizing
the vast amount of energy required to change a material’s state. The reasonably high heat of fusion
and relatively small volumetric change of solid-liquid phase transition in comparison to solid-solid
and liquid-gas transitions make it well suited for various TES applications. Numerous materials
have been investigated as potential phase change materials (PCM) over a wide range of temperatures
including paraffin wax, fatty acids, NaNO3 , KNO3 , NaNO3 –KNO3 eutectics, NaCl, and sodium borate
oxides [1,4–6]. Ushak et al. [7] and Gomez et al. [8] reviewed the appropriate usage of some molten

Energies 2018, 11, 572; doi:10.3390/en11030572 www.mdpi.com/journal/energies

Energies 2018, 11, 572 2 of 18

salts along with other storage media in TES systems including Hitec solar salt, mineral oil, synthetic oil,
silicone oil, nitrate salts, carbonate salts, and liquid sodium. However, most of the studied materials
had a low solid thermal conductivity which vastly reduces the heat transfer rate during solidification.
Research into various means of increasing the heat transfer rate is a wide topic that includes embedding
a highly conductive material into the PCM [9–14], encapsulation [4,5,15–22], embedding fins into the
PCM [23–25], and using heat pipes [26–35].
In the development of a TES system, one of the major challenges is the appropriate selection of
materials for the construction of the salt container. Key requirements include strength and corrosion
resistance at elevated temperatures, raw material cost, commercial availability, and manufacturability
using common fabrication methods. Kuravi et al. [2] provided a list of materials that are suitable
for use in TES systems based on the type of PCM salt utilized and the operating temperatures.
These materials include (but are not limited to) AISI 1015 carbon steel, AISI K01200, stainless steel
304, stainless steel 316, A36 carbon steel, and high nickel alloys. Zhao et al. [5] reported that there
was no degradation of a MgCL-SS304 encapsulated PCM capsules after prolonged exposure to high
temperatures. Zahrani and Alfantazi [36] presented their findings on the corrosion behavior of Inconel
625 in a PbSO4 –Pb3 O4 –PbCl2 –Fe2 O3 –ZnO molten salt environment. The mixture of the molten salt was
tested in the air at temperatures of 600, 700, and 800 ◦ C. They identified the following as corrosion attack
modes: the formation of voids, general surface corrosion, intergranular corrosion, internal oxidation and
sulfidation, and a network of distributed pores on the surface and the cross-section. Sarvghad et al. [37]
conducted a compatibility study of SS 316, duplex steel 2205, and carbon steel 1008 with NaCl–Na2 CO3 at
700 ◦ C and Li2 CO3 –K2 CO3 –Na2 CO3 at 450 ◦ C in air for TES. Stainless steel 316 displayed the greatest
resistance to corrosion due to the formation of films on its surface. At 450 ◦ C, the corrosion mechanism
for all alloys considered was uniform without localized attack. At 700 ◦ C, oxidative attacks on grain
boundaries were the primary corrosion mechanism. A review of the literature by Gil et al. [1] indicated
that the corrosion rate of stainless steel is increased by approximately 25–50% during thermal cycling
compared to isothermal immersion in molten nitrate salts and that the chloride content of the molten
salt has an impact on the corrosion rate. The authors also state that carbon steels may be considered
as potential TES containers in applications where exposure to nitrate salts can be limited to less than
400 ◦ C. Liu et al. [38] conducted a study of isothermal corrosion of TP347H, C22 alloy, and laser-cladding
C22 coating in molten alkali chloride salts in air at 450–750 ◦ C. Gomez-Vidal and Tirawat [39] presented
the results of corrosion tests for several alloys in a eutectic molten chloride solution at 650–700 ◦ C in
a nitrogen atmosphere. The alloys tested included stainless steel 310, stainless steel 347, Incoloy 800H,
and Inconel 625, with Inconel 625 having the greatest corrosion resistance at 2.80 ± 0.38 mm/year.
Sarvghad et al. [40] examined the compatibility of Inconel 601 with NaCl–Na2 CO3 and NaCl–Na2 SO4 at
700 ◦ C in air. They also studied the compatibility of Inconel 601 withLi2 CO3 –K2 CO3 –Na2 CO3 at 450 ◦ C
in air. It was determined that oxidation was the primary mechanism leading to oxide deposits on the
oxide surface, and de-alloying was detrimental to the material to 700 ◦ C, with the availability of oxygen
controlling its rate.
The material compatibility study was conducted to determine the suitability of two metal alloys
for TES vessels containing a phase-change material. The PCM used in the study was a NaF–NaCl
eutectic mixture. This NaF–NaCl eutectic mixture was chosen as PCM due to (1) extremely low
cost; (2) availability; (3) the melting temperature of 680 ◦ C, which is close to the optimal operating
temperature of the commercially available Stirling engine used for the project. Most of the PCM
studied in the past was for an operating temperature much lower than what we were looking for.
Other materials, such as liquid metals are good for a high operating temperature, but the cost is too
high. The long-term testing data for this specific eutectic mixture of NaF–NaCl was not available.
The closest PCM materials for high temperature TES are the ones used for NASA Solar Dynamic Space
Power Systems in the 1980s [41]. NASA data was used as the guidance for our selection of the PCM
and sample container materials and the testing, but no direct comparison could be made.
Energies 2018, 11, x572
2018, 11, 3 of 18

CSP with Dish Stirling has been explored over many years as it offers excellent prospects for
massCSP with Dish
production Stirling has
of low-cost, highbeen explored
efficiency overpower
electric many[3,42]
yearsand
as itTES
offers
has excellent
begun to prospects
be integratedfor
mass production of low-cost, high efficiency electric power [3,42] and TES has begun
with these systems [43,44]. For a typical integrated TES/CSP system, sunlight is directed onto the to be integrated
with
TES these systems
receiver [43,44]. For
via mirrors on aatypical integrated
parabolic dish TES/CSP system,
concentrator. sunlight
A heat is directed
transport ontosuch
device the TESas
receiver via mirrors on a parabolic dish concentrator. A heat transport device such as
high-temperature heat pipes or a pump loop system is often used to transfer thermal energy to the high-temperature
heat pipes
PCM. This or a pump
heat loopdevice
transport system is often
also usedheat
transfers to transfer thermalengine
to the Stirling energyduring
to the PCM
PCM.discharge.
This heat
transport
Figure 1 device
shows alsothe transfers
integratedheat to Stirling
dish the Stirling
CSPengine
system during
with PCM
a TES discharge.
module. Figure 1 shows
The operating
the integrated dish Stirling CSP system with a TES module. The operating temperature
temperature of the TES module varies from local ambient to 700 °C due to solar insolation variations of the TES
module varies ◦
throughout thefrom
day. local
To beambient to 700 ofCadue
representative TEStosystem,
solar insolation
the test ofvariations throughout
the TES material samplesthe was
day.
To be representative of a TES system, the test of the TES material samples was operated at 750 ◦ C.
operated at 750 °C.

Figure 1. Integrated TES and Dish Stirling CSP.

Figure 1. Integrated TES and Dish Stirling CSP.
2. TES Vessel Material Selection
2. TES Vessel Material Selection
Molten salts are used in a variety of fields including nuclear, air and space, as well as solar
power Molten salts are
generation. Anused in a variety
extensive reviewof of
fields
the including
literature nuclear, air and space,
was performed as well
to evaluate theasapplicability
solar power
generation. An extensive review of the literature was performed to evaluate the
for their use in a TES system. The data gathered from NASA Solar Dynamic Space Power Systems applicability for their
use in a TES system. The data gathered from NASA Solar Dynamic Space Power Systems
Program have the closest similarities to the current TES as they used alkali halide salt based PCM at Program
have operating
high the closesttemperature.
similarities Atodown-select
the current process
TES as they usedinalkali
resulted halide salt
five candidate based PCM
materials at high
for potential
operating temperature. A down-select process resulted in five candidate materials for potential
use as the TES container material with alkali halide salt based PCM. Of these five materials, stainless use
as the316L
steel TES(SS316L)
container material
and Inconelwith
625 alkali halide salt
were selected for based
testingPCM.
becauseOf of
these five
their rawmaterials,
material stainless
cost and
steel 316L (SS316L) and Inconel 625 were selected for testing because of their raw
availability. Although numerous compatibility studies have previously been conducted with alkali material cost and
availability. Although numerous compatibility studies have previously been conducted
fluoride salt mixtures, studies of NaF–NaCl eutectic mixtures were not found. Based on the chemical with alkali
fluoride saltofmixtures,
similarities studies
the chosen of NaF–NaCl
salt with eutectic studies,
those in previous mixturesthe
were not found.
previous Based
studies onused
were the chemical
to guide
the current material section. The results of previous alkali fluoride salt material compatibilitytostudies
similarities of the chosen salt with those in previous studies, the previous studies were used guide
the current material section. The results
are summarized in the following points: of previous alkali fluoride salt material compatibility studies
are summarized in the following points:
Energies 2018, 11, 572 4 of 18

Energies 2018, 11, x 4 of 18

• High-temperature alloys can be used as containers for molten salt TES. Most notably, Inconel 617
• High-temperature alloys can be used as containers for molten salt TES. Most notably, Inconel
and stainless steel 304 have demonstrated limited degradation with no signs of failure even after
617 and stainless steel 304 have demonstrated limited degradation with no signs of failure even
five years of thermal cycling.
after five years of thermal cycling.
•• Oxygen,
Oxygen,
water
Energies
Energies
water
residue,
2018,2018,
11, x11, x
residue,
and
and
sodium
Energies 2018, 11,cations
sodium x
cations
are the three oxidizing agents present in4 the
are the three oxidizing agents present4 ofin18 of 18 PCM
the PCM 4 of 18
salt system.
salt system.
• • High-temperature
High-temperature • alloys
alloys can can be used
High-temperature
be used asalloys
containers
as containers can for
forbemolten molten
used as
salt salt
TES.TES.
containers Most Most notably,
fornotably,
molten saltInconel
InconelTES. Most notably, Inconel
•• Over
Over time,
time,617 the
the
617
and
corrosion
corrosion
and stainless
stainless
rate
rate
steel steel
304
of
617
the
of304the
have have
and
metallic
metallic
demonstrated
demonstrated
stainless
alloys
alloys
steel
in
304limited
limited
have
aademonstrated
molten
indegradation
moltenwith
degradation salt
salt will
nowill
with
limited
decelerate
decelerate
no degradation
signssigns of failure
of failure even
due
due
with
to
noto
even the
theof failure even
signs
limited availability
afterafter
five of
five
years strong
years
of of
thermal oxidizing
thermal
limited availability of strong oxidizing agents.after cycling.
cycling.
five agents.
years of thermal cycling.
•• • • Oxygen,
Minimizing Oxygen, waterwater •
residue,
residue, and and
Oxygen,
sodiumsodium
water cations
cations are are
residue, the
and the
threethree
sodium oxidizing
oxidizing
cations areagents
agents the present
ispresent
three in the
oxidizing
in the PCM PCMof
agents present in the PCM
Minimizing the the levels
levels of
of oxygen
oxygen and and water
water vapor
vapor inside
inside aa TES
TES vessel
vessel is crucial
crucial to to the
the lifelife of the
the
salt salt system.
system. salt system.
hardware.
hardware. Corrosion
Corrosion can
can cause
cause material
material failure
failure in in
under
under a weeka weekif significant
if significant traces of water
traces of and
water
• • Over Over
time,time,
the the •
corrosion
corrosion raterate
Over of
time, of the
the the metallic
metallic
corrosion alloys
alloysrate ainmolten
in of a molten
the salt salt
metallic will will
alloys decelerate
decelerate
in duedue
a molten to to
saltthe thedecelerate due to the
will
oxygen
and oxygenarelimited
present.
are present.
limited availability
availability oflimited
of strong strong oxidizing
oxidizing
availability agents.
agents.
of strong oxidizing agents.
•• Due
Due toto•low• Minimizing
low electronegativity
Minimizing the the
electronegativity •levels
levels amongst
of oxygen
ofamongst
Minimizing
oxygen the
and the elements
and
the water
levels
water vapor
elements of present
vapor
oxygeninside
inside
present aandina water
TES the
TES material,
vessel
vessel
in the vapor isinside
ismaterial,
crucial sodium
crucial to
toathe
TESthe
life
sodium cations
life
vessel
of theofistheare not
crucial
cations to the life of the
are
expected to behardware.
hardware.
an active Corrosion
Corrosion can
oxidizer can cause
hardware.
cause
within material
material
Corrosion
the failure
failure
system.canin in
cause
underunder a
material
a weekweek
failure
if if significant
significant
in under traces
traces
a week
of of
water
if water
significant traces of water
not expected to be an active oxidizer within the system.
andand oxygen
oxygen are are present.
present. and oxygen are present.
• Due
Table 1• lists
lists Due
the
the to low
toalloys
low
alloys that•were
electronegativity
electronegativity
that Due
were amongst
amongst
to low
initially
initially the elements
electronegativity
the elements
considered
considered for present
present
amongst
for in
useuse in
intheinthe
the
the material,
material,
elements
the
TESTES sodium
sodium
present
module.
module. cations
cations
in
Duethe are
material,
arehigh
Due
to sodium cations are
to high
cost,
not not expected
expected to betoan
beactive
annot
active oxidizer
oxidizer
expected within
within
to be an the system.
theactive
system.
oxidizer within the system.
cost, lack
lack of of availability,
availability, andand manufacturing
manufacturing difficulties,
difficulties, Hastelloy
Hastelloy N,N,Inconel
Inconel617,617,and
and Incoloy
Incoloy 800HT
were eliminated. Table
Table 1 lists
1 lists the alloys
the alloys thatthat
Table
werewere
listsinitially
1 initially considered
the considered
alloys that were for
for use use in considered
initially
in the the
TESTES module.
module. useDue
forDue to to high
inhigh
the TES cost,
cost,module. Due to high cost,
eliminated.
lacklack of availability,
of availability, andand
lack manufacturing
manufacturing
of availability, difficulties,
difficulties, Hastelloy
and manufacturing
Hastelloy N, Inconel
N,difficulties,
Inconel 617,617,
andand
Hastelloy Incoloy
Incoloy
N, 800HT
Inconel
800HT 617, and Incoloy 800HT
werewere eliminated.
eliminated. were eliminated.
Table 1. TES vessel material candidates.
Table 1. TES vessel material candidates.
Table
Table 1. TES
1. TES vessel
vessel material
material
Table candidates.
candidates.
1. TES vessel material candidates.
Candidate
Candidate Material Alloy
Material Alloy Ni
Ni FeFe+ +
CrCr $ Rank
$ Rank
Candidate MaterialAlloy
Candidate
Stainless Steel Material
316L Fe–CrAlloy Ni Ni
Candidate
Low +Fe
FeHighCr+ Cr
Material $ RankNi
$Alloy
Rank
Low Fe + Cr $ Rank
Stainless Steel 316L
Stainless
Stainless Fe–Cr
SteelSteel
316L 316LFe–Cr
Fe–CrLow
LowLow
Stainless High
SteelHigh LowLowLow
HighFe–Cr
316L Low High Low
Incoloy
Incoloy 800HT
800HT Incoloy
Incoloy 800HT800HT Ni–Fe
Ni–Fe Ni–Fe
Ni–Fe Incoloy 800HT Ni–Fe
Inconel
Inconel 617 617Inconel
Inconel 617 617 Ni–Cr
Ni–Cr Ni–Cr
Ni–Cr Inconel 617 Ni–Cr
Inconel 625
Inconel Inconel
625
Inconel 625 625
Ni–Cr
Ni–Cr Ni–Cr
Ni–Cr Inconel 625 Ni–Cr
Hastelloy N
Hastelloy
Hastelloy N N Hi
Hastelloy N NiHi Ni High
Hi Ni
Hastelloy
Hi Ni High N Low
HighHigh Low Low Hi
Low High High
NiHigh
HighHigh Low High

3. Sample
3. Sample Preparation
Preparation and and Testing
3. Sample
TestingPreparation and Testing
3. Sample Preparation and Testing
Testing
Figure
Figure 2 shows
2 shows a sample
a sample container
Figure
container withwith
2 shows aan an interior
sample
interior volume
container
volume withofanmL,
of 35 35interior
mL, fabricated
fabricated
volume out
outof ofmL,
of35bothboth
fabricated out of both
Inconel
FigureInconel
2 shows 625 625
andand
a samplestainless
stainless steelsteel
container
Inconel 316L.
316L.
625 To
and To
with
avoidavoid
an
stainless contamination,
interior
contamination, volume
steel 316L. To the
endend
theavoid of
caps caps
35 and
mL,
contamination,
and afabricated
a small small
the fill tube
fill end
tube out
caps
werewere
ofa both
and small fill tube were
electron
electron beam beam welded
welded to to the
electron
the cylindrical
cylindrical
beam weldedbody.
body. Using
to Using
the the the fill tube,
cylindrical
fill tube, body.
salt salt
was was
Using added
added
the fill
to to the
the
tube, container.
container.
salt was added to the container.
Inconel 625 and stainless steel 316L. To avoid contamination, the end caps and a small fill tube were
TheThe fill tube
fill tube waswas crimped
crimped The and
andfill sealed
sealed
tube was
usingusing fusion
crimped
fusion andwelding
welding
sealed
after after
the the
using samples
samples
fusion welding
were were
filled.filled.
after the samples were filled.
electron beam welded to the cylindrical body. Using Using the the fill
fill tube,
tube, salt
salt was
was added
added to to the
the container.
container.
The fill tube
tube was
was crimped
crimped and and sealed
sealed usingusing fusion
fusion welding
welding afterafter the the samples
samples were werefilled. filled.

Figure
Figure 2. A2. A sample
sample container
container
Figure for compatibility
for compatibility
2. A testing.
sample container
testing. for compatibility testing.

TheThe sample
sample containers
containers were
Thewere
first
samplefirst cleaned
cleaned in ain
containers a solvent
solvent
were first
using using
cleaned ultrasonic
ultrasonicin a solventagitation
agitation andand
using deionized
ultrasonic
deionized agitation and deionized
water.
water. TheThe samples
samples werewere
water.
dried dried
The
using using
samples nitrogen
nitrogen were gas
andand
gasdried then then
using baked-out
baked-out
nitrogen at at
gas200 200
and °Cthen°C over
for for over
baked-out3 h 3under
hatunder
200 °C for over 3 h under
atmospheric
atmospheric conditions
conditions in in oven.
an oven.
atmospheric
an AfterAfter
conditions
bakingbaking anunder
inunder oven. atmospheric
atmospheric
After baking conditions,
conditions, the the
under atmospheric samples
samples were the samples were
conditions,
were
heated
heated for 4for 4 h400
h at
Figure
Figure
at 400 °C
°C in
2.
2.
ain
heated
A
Aa sample
sample
vacuum
vacuumfor 4 furnace
container
h atcontainer
furnace
400at °C1.6
in
for
afor
at ×1.610
vacuum
compatibility
×−4compatibility
10Torr. furnace
testing.
−4 Torr. In an testing.
ateffort
In an effort to−4minimize
1.6to×minimize
10 Torr. excess
In an excess
effort
oxygenoxygen
to minimize excess oxygen
andand water
water contaminants
contaminants and
beforebefore
water filling
filling the the
contaminants samples,
samples, the the
before salt salt
filling
PCM PCM
the constituents
constituents
samples, thewere were
salt heated
PCM heated to 200
constituents
to 200 °C °C were heated to 200 °C
The sample
by aby acontainers
hotplate
hotplate in ain a were
gloveglove
box first
by abox
for forcleaned
h.10The
hotplate
10 h. The
in in
asample
glove abox
sample solvent
containers
containers
for 10 h.using
were
Thewere ultrasonic
filled
filled
sample with with
containersaagitation
NaF–NaCl
a NaF–NaCl weremixture and
mixture
filled deionized
with
at aatNaF–NaCl mixture at
The sample 4N
containers
grade (99.99%
were
purity).
firstThe
cleaned
filling
in aconducted
solvent inusing ultrasonic agitation and deionized
water. The 4N grade
samples (99.99%
were purity).
dried 4N The
usinggrade
filling
(99.99%
nitrogen waswas purity).
conducted
gas and Thein thenthe the
filling glove
wasglove
baked-out box.box.
conducted
The atThe in volume
volume
200 the forchange
glove
change box.
upon upon
The
3 h volume
under change upon
water. The samples were dried using nitrogen gas and then baked-out at 200 ◦°C
C for
over
over 3 h under
melting
melting waswas accounted
accounted for for when
melting
when was filling
filling the the
accounted samples.
samples.
for when TheThe container
container
filling the was was
samples. oversized
oversizedThe container to accommodate
to accommodate was oversized to accommodate
atmospheric conditions in an oven. After baking under atmospheric conditions, the samples were
atmospheric theconditions
the thermal
thermal in
expansion an oven.
expansion of of
thePCM After
PCM
thermal
from frombaking
expansion
solid solid under
to PCM
to molten
of molten atmospheric
salt salt
fromat theat the
solid desired conditions,
todesired
molten operating
operating the samples
temperature.
salt attemperature.
the desired were
operating temperature.
heated for 4 h The
at 400PCM◦°C in a vacuum furnace at 1.6 × 10 −4 Torr. In an effort to minimize excess oxygen
heated for 4The
h atPCM
400 C was
was in ainitially
initially
vacuumThe inPCM
in powder powder
furnace was
form form 1.6with
initially
atwith very
×in10 very−4 low
powder
low compaction
compaction
Torr.formIn with factor.
factor.
an effortvery low The
Theminimize
to PCM
compaction
PCM filling
filling waswas
factor.
excess The PCM filling was
oxygen
and water contaminants
accomplished
accomplished by before
by taking
taking filling
several
accomplished
several the
steps. samples,
steps.
Each Each
by taking
time,time,theonly
several
only asalt a PCM
portion
steps. of constituents
portion
Each of
PCM PCM
time, powder
powder
only were
a portion
was wasfilledheated
filled
of intointo
PCM the to
the200was
powder °C filled into the
and water contaminants
container
before filling the samples, thethe saltcontainer
PCM constituents were heated melt to 200 ◦ C
container
by a hotplate in andand
a glove abox a for
band band 10heater
heater
container The wrapped
h. wrapped
and a around
sample band around
heater
the container
containers wrappedwere was was
aroundturned
filled turned
the
with on aon
container to let
toNaF–NaCl
let wasPCM
PCM turned
meltmixtureon toatlet PCM melt
by a hotplate in a glove box for 10 h. The sample containers were filled with a NaF–NaCl mixture
4N grade (99.99% purity). The filling was conducted in the glove box. The volume change upon
at 4N grade (99.99% purity). The filling was conducted in the glove box. The volume change upon
melting was accounted for when filling the samples. The container was oversized to accommodate
melting was accounted for when filling the samples. The container was oversized to accommodate the
the thermal expansion of PCM from solid to molten salt at the desired operating temperature.
thermal expansion of PCM from solid to molten salt at the desired operating temperature. The PCM
The PCM was initially in powder form with very low compaction factor. The PCM filling was
accomplished by taking several steps. Each time, only a portion of PCM powder was filled into the
container and a band heater wrapped around the container was turned on to let PCM melt
Energies 2018, 11, 572 5 of 18

was initially in powder form with very low compaction factor. The PCM filling was accomplished
by taking several steps. Each time, only a portion of PCM powder was filled into the container and
a band heater wrapped around the container was turned on to let PCM melt completely. The band
heater was shut off after the melting to let the PCM cool down until it completely solidified to high
compaction solid. This process was repeated until the container was filled with the desired amount of
PCM. The filling process was conducted in a glove box. The glove box can provide environmental
conditions of O2 <10 ppm and H2 O <10 ppm. Once the samples were filled the container had the
vacuum pulled down to 10−6 Torr. A hydraulic crimping tool was used to punch the fill tube. After the
punch, the fill tube was cut and fusion welded across the crimp.
Multiple samples of both Inconel 625 and stainless steel 316L were fabricated and then heated in an
oven to 750 ◦ C. The melting temperature of the NaF–NaCl eutectic salt is around 680 ◦ C. Although the
outer surfaces of the containers were exposed to ambient condition, the interior salt is under a 10−6 Torr
vacuum. The samples were held at 750 ◦ C for 100 or 2500 h at which point they were taken out from the
oven for examination.

4. Test Results and Discussion

After 100 and 2500 h of heating, the Inconel 625 and stainless steel 316L samples were taken out
from the furnace and then cut open. Scanning electron microscopy (SEM) and energy dispersive X-ray
spectroscopy (EDX) were used to analyze the interior surface and the cross-section of the containers.
Other techniques for characterizing the samples were also explored. It would be better if both the
vessel materials and the PCM were examined. The dissolution of the chemical elements of the vessel
materials into the PCM can be better characterized by conducting a chemical analysis on the molten
salt. Additionally, examining the molten salt may further aid the study of the impact of the dissolved
chemical elements on the degradation of the molten salt’s performance. Note that this paper will only
present the measurements and analysis results of the container materials as the focus of the project was
on the container materials. The primary chemical compositions of both stainless steel 316L and Inconel
625 were measured from the same material batch used for the fabrication of the sample containers.
Tables 2 and 3 present the key alloy compositions of the unheated materials.

Table 2. Chemical composition of SS 316L, raw material prior to fabrication.

Sample Material C Fe Cr Ni Mo Mn Cu
SS 316L 0.21% 78% 16.5% 10.1% 2.05% 1.7% 0.43%

Table 3. Chemical composition of Inconel 625, raw material prior to fabrication.

Sample Material C Fe Cr Ni Mo Nb Al
Inconel 625 0.005% 1% 20.5% 66% 8.3% 3.38% 0.21%

A sample from the side wall of the vessel that was near the end cap and the weld zone was used
for SEM. The sample was mounted on the holder using carbon coated, conductive adhesive tape.
A Quanta 3D FEG by FEI Corp was used for SEM analysis.
An unused sample container was used to develop a baseline for comparison and therefore was
analyzed first. No corrosion was observed, as expected the surface was protected by a chromium
oxide layer. However, a top surface EDX analysis revealed that there was an enrichment of manganese
and copper, Table 4. Of all of the alloy constituents, manganese and copper have the highest
vapor pressure at elevated temperatures [45]. Thus it is probable that the elements preferentially
evaporated during the welding process and were then re-deposited on to the surface during cooling.
To gain a better understanding of how the microstructure and chemical composition of the raw
stainless steel 316L material were impacted by both machining and the electron beam welding process,
Energies 2018, 11, 572 6 of 18

an in-situ ion milling process was performed using focused ion beam technology to obtain detailed
information from the cross-section of the samples. First, the alloy cross-section surface was roughly
milled by the ion beam and then finely polished/etched by the secondary ion beam to expose the
underlying microstructural details. The surface morphology of the untested sample is shown in
Figure 3. The defects seen in Figure 3 are machining marks.

Table EDX
Energies4.2018, 11,chemical
x analysis and key element concentration at SS316L surface after machining and
6 of 18
Electron Beam welding, untested.
Table 4. EDX chemical analysis and key element concentration at SS316L surface after machining
Energies 2018, 11, x 6 of 18
and Electron Beam welding, untested.
Sample Material O Fe Cr Ni Mn Cu
Table 4. EDX chemical
SSanalysis
Sample
316L and key O
Material element
1.6% Feconcentration
46% Cr
18.4% Ni at SS316L
5% surface after machining
Mn23%Cu 2%
and Electron Beam welding, untested. 1.6% 46% 18.4% 5% 23% 2%
SS 316L

Sample Material O Fe Cr Ni Mn Cu
SS 316L 1.6% 46% 18.4% 5% 23% 2%

Figure 3. Top-down SEM image of an untested SS 316L sample surface (5000×).

Figure 3. Top-down SEM image of an untested SS 316L sample surface (5000×).
An SEM image of the cross-section of the untested stainless steel 316L sample is presented in
Figure 3. Top-down SEM image of an untested SS 316L sample surface (5000×).
Figure
An SEM 4. Between
image of thethe
sample surface and
cross-section ofthe
thedeposited
untestedcarbon protection
stainless layer,sample
steel 316L a half micron thick in
is presented
layer
Figure 4. Ancan be
Between seen.
SEM image In Figure
the sample 4, the top layer
surface and of
of the cross-section is
the the
the deposited
deposited carbon layer used
carbon protection
untested stainless to protect the
layer, aishalf
steel 316L sample material
micron
presented inthick
during
Figure theBetween
4. ion milling
the process.surface
sample The manganese
and the content of
deposited the layer
carbon was further
protection layer, confirmed
a half by thick
micron EDX
layer can be seen. In Figure 4, the top layer is the deposited carbon layer used to protect the material
analysis
layer and seen.
a level
Inof over 20% thewas measured.
layer is theThis further carbon
confirms thatused
the enrichment of material
Mn and
during thecan
ionbemilling Figure
process. 4, The top
manganese deposited
content layer
of the layer to protect
was further the
confirmed by EDX
Cu at
during the
thesurface results
ion milling from
process.the metal elements
Themeasured.
manganeseThis being
contentvaporized during
of theconfirms the
layer wasthat electron
further beam welding
confirmed byofEDX
analysis and
process a level of over 20% was further the enrichment Mn and
analysisandandwere then
a level deposited
of over 20% was back onto the substrate.
measured. This further confirms that the enrichment of Mn and
Cu at the surface results from the metal elements being vaporized during the electron beam welding
Cu at the surface results from the metal elements being vaporized during the electron beam welding
process and were then deposited back onto the substrate.
process and were then deposited back onto the substrate.

Figure 4. Cross-section SEM image of untested SS 316L sample, (20,000×).

4.1. Stainless Steel 316L, 100 H Test

Figure 4. Cross-section SEM image of untested SS 316L sample, (20,000×).
Figure
The interior 4. Cross-section
surface SEM
of a stainless image
steel 316Lof untested
sample SS100
after 316L sample,
h of (20,000
heating ×). in Figure 5.
is shown
4.1. Stainless
The sample forSteel 316L, 100 Hwas
examination Testselected at a location far from the weld zone. A significant amount
4.1. Stainless Steel can
of roughness 316L,
be 100
seenHonTest
the sample’s surface. Both grain boundaries and polycrystalline grains
The interior surface of a stainless steel 316L sample after 100 h of heating is shown in Figure 5.
are visible. The homogeneous surface roughness and a shallow V-shaped groove on corrosion sites
The sample
The interiorfor examination
surface was selected
of a stainless steelat316L
a location
sample far after
from 100
the weld
h of zone. A significant
heating is shownamount
in Figure 5.
indicate that corrosion
of roughness progressed
can be seen on the uniformly
sample’s in all directions.
surface. Both grain The least desired
boundaries form of corrosion
and polycrystalline for
grains
The sample for examination was selected at a location far from the weld zone. A significant
TES applications is unidirectional corrosion penetration along a grain boundary. This type of
amount of
are visible. The homogeneous surface roughness and a shallow V-shaped groove on corrosion sites
corrosion progresses
indicate that corrosionmainly in theuniformly
progressed Z direction
in along the grainThe
all directions. boundary and the
least desired formmetal loss within
of corrosion for
the grains is insignificant. It is undesirable because even a very small amount
TES applications is unidirectional corrosion penetration along a grain boundary. This of metal losstype
could
of
reduce theprogresses
corrosion material thickness
mainly in significantly,
the Z directionresulting
along theingrain
earlyboundary
failure. This
and was not seen
the metal in the
loss within
examined
the grains sample. The morphology
is insignificant. seen further
It is undesirable becauseindicates that small
even a very two localized
amount of metal
metal dissolutions
loss could
reduce the material thickness significantly, resulting in early failure. This was not seen in the
Energies 2018, 11, 572 7 of 18

roughness can be seen on the sample’s surface. Both grain boundaries and polycrystalline grains are visible.
The homogeneous surface roughness and a shallow V-shaped groove on corrosion sites indicate that
corrosion progressed uniformly in all directions. The least desired form of corrosion for TES applications is
unidirectional corrosion penetration along a grain boundary. This type of corrosion progresses mainly in the
Z direction along the grain boundary and the metal loss within the grains is insignificant. It is undesirable
because even a very small amount of metal loss could reduce the material thickness significantly, resulting
in early failure. This was not seen in the examined sample. The morphology seen further7 indicates
Energies 2018, 11, x of 18
that two localized metal dissolutions started: pitting and inter-granular. The dissolution level changes
profoundly
started: along
pittingtheandgrain boundaries,
inter-granular. The but the majority
dissolution had a very
level changes small amount
profoundly along theof corrosion.
grain At grain
boundaries,
butEnergies
boundary the majority
junctions,
2018, 11, x had
the a very
corrosionsmall
pits amount
were of
also corrosion.
observed. At grain
This boundary
suggests that junctions,
all the
localized corrosion
attacks
7 of 18 started
pits were also observed. This suggests that all localized attacks started at
at the boundaries. Lastly, corrosion products were found in the sample substrate. This indicatesthe boundaries. Lastly, that
corrosion
started: products
pitting and were found
inter-granular. in
Thethe sample
dissolution substrate.
level changes This indicates
profoundly alongthat
the
dissolution of the corrosion products into the molten salt occurred via Louis acid reaction process dissolution
grain of between
boundaries, the
but the majority
corrosion productshad intoa very small amount
the molten of corrosion.
salt occurred At grain
via Louis acidboundary
reaction junctions, the corrosion
process between the hot
the hot molten inorganic halides and the surface oxide [46,47].
pits were
molten also observed.
inorganic This
halides and thesuggests
surface that all[46,47].
oxide localized attacks started at the boundaries. Lastly,
corrosion products were found in the sample substrate. This indicates that dissolution of the
corrosion products into the molten salt occurred via Louis acid reaction process between the hot
molten inorganic halides and the surface oxide [46,47].

(a) (b)
Figure 5. (a) Top-down and (b) tilted SEM images of SS 316L sample surface after 100 h heating (5000×).
Figure 5. (a) Top-down and (b) (b) after 100 h heating (5000×).
(a) tilted SEM images of SS 316L sample surface
Figure
Figure6 5.
shows the four
(a) Top-down sample
and surface
(b) tilted locations
SEM images selected
of SS 316L forsurface
sample EDX after
chemical analysis.
100 h heating The results
(5000×).
of the EDX analysis are presented in Table 5. The distribution
Figure 6 shows the four sample surface locations selected for EDX chemical analysis. of salt particles and surface oxide
Theonresults
the Figure
sample 6 shows
surface the four
were not sampleInsurface
even. Figure locations
5 the selected
dark areasfor EDXlow
have chemical
oxygen analysis.
and The results
sodium levels,
of the EDX analysis are presented in Table 5. The distribution of salt particles and surface oxide on
of the EDX
indicating analysistoare
minimal nopresented
oxide orInin Table
salt 5. TheThe
present. distribution
levels ofofsodium,
salt particles and surface
oxygen, andand oxide on
fluorine were
the sample surface werewere not even. Figure 55 the
thedark
dark areas have low oxygen sodium levels,
undetectable at site 1 indicating no salt and oxide in this area. Both sites 2 and 3 showlevels,
the sample surface not even. In Figure areas have low oxygen and sodium a slight
indicating minimal
indicating minimalto no to oxide
noNot or or
oxide saltsaltpresent.
present. Thelevels
The levels of sodium, oxygen, and fluorine
were were
amount of salt and oxide. only does site 4 have typical of sodium,
salt oxygen,
morphology andoxygen,
with fluorine fluoride,
undetectable at
undetectablesite 1
at indicating no
site 1 indicating salt
no and oxide
salt and in
oxide this area.
in this Both
area.
and sodium concentrations over 10%, but also a chromium enriched surface oxide is present.
sites
Both sites2 and
2 and3 3show
showaaslight
slight amount
amount
of saltNoteworthy
and of salt
oxide. and oxide. Not only does typical
site 4 have typical salt morphology with oxygen, fluoride, sodium
isNot
the only does
enrichment site 4 have
of molybdenum at salt
sitesmorphology
1 and 2 and the with oxygen,
manganese fluoride,
depletion and at sites
and
concentrations sodium concentrations over 10%, but also a chromium enriched
over 10%, but also a chromium enriched surface oxide is present. Noteworthy surface oxide is present. is the
1 to 3.
Noteworthy is the enrichment of molybdenum at sites 1 and 2 and the manganese depletion at sites
enrichment of molybdenum at sites 1 and 2 and the manganese depletion at sites 1 to 3.
1 to 3.

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

Figure 6. Cont.
Energies 2018, 11, x 8 of 18
Energies 2018, 11, 572 8 of 18

Energies 2018, 11, x 8 of 18

(c) (d)
(c) (d)
Figure 6. Selected sites on SS316L sample surface for EDX analysis: (a) Sample location 1; (b) Sample
Figure 6. Selected
Figure 6.
location 2; (c)sites on SS316L
SS316L3;sample
onlocation
Sample sample surface
surface
(d) Sample for
for4.EDX
location EDX analysis:
analysis: (a) Sample location
location 1;1; (b)
(b) Sample
Sample
location
location 2;
2; (c)
(c) Sample
Sample location
location 3;
3; (d)
(d) Sample
Sample location
location 4.
4.
Table 5. EDX chemical analysis, weight percentage of SS 316L sample surface after 100 h testing.
Table
Table 5. 5.
EDXEDX chemical
chemical analysis,
analysis,
Sample Site O% weight
weight percentage
F%percentage
Na% Fe% ofof
SSSS 316Lsample
316L
Cr% sample
Ni% surface
surface
Mo% after100
after
Mn% 100h htesting.
testing.
1 - - - 71 11.62 10.9 6 -
Sample Site O% F% Na% Fe% Cr% Ni%10.2Mo%- Mn%
Sample Site2 O% 2.55F% - Na%- Fe% 61 10.54
Cr% 8.7 Ni% Mo% Mn%
1 3 - 1.78 - - -
1.57 71 11.24
70 11.62 10.310.9 3 6 - -
1 2 4 -2.5511 - -13.4 - 16.7
- 71
11.5 11.62
61 33.06 10.9 - 10.262.1
10.54 1.6 8.7 - -
2 2.55 - - 61 10.54 8.7 10.2 -
3 1.78 - 1.57 70 11.24 10.3 3 -
3
Figure 7 shows a 1.78
cross-section -view 1.57
of the 70 after
sample 11.24
100 h 10.3 The 3micro-voids
heating. -
4 4 1111 13.4 13.4 16.716.7 11.5
11.5 33.06
33.06 1.6
1.6 - - 2.12.1 resulting
from element depletion were not visible. The deep grain boundary corrosion penetration was not
present. As a result of annealing, grain recrystallization and growth occurred replacing the refined
Figure 7 shows
and highly a cross-section
distorted grains seenview of the
in the sample
untested after 100
sample. This hisheating.
desirableThe micro-voids
because resulting
the larger
fromFigure
element7 shows a cross-section view ofThethe sample afterboundary
100 h heating. The micro-voids resulting
annealed grains are more stable and thus provide a higher resistance to corrosion than that of thewas not
depletion were not visible. deep grain corrosion penetration
from element
present.grains depletion
As athat
result were not
of annealing,
are plastically visible.
grain recrystallization and growth occurred replacing the present.
deformed. The deep grain boundary corrosion penetration was not refined
As
anda result
highlyof distorted
annealing,grains
grain recrystallization and growth
seen in the untested occurred
sample. This is replacing thebecause
desirable refined and
the highly
larger
distorted grains seen in the untested sample. This is desirable because the larger annealed
annealed grains are more stable and thus provide a higher resistance to corrosion than that grains areof
more
the
stable and thus provide a higher resistance
grains that are plastically deformed. to corrosion than that of the grains that are plastically deformed.

Figure 7. Cross section SEM image (12,000×).

The cross section of the 100 h stainless steel 316L sample was analyzed with EDX to characterize
the key elements concentration. Performing EDX on the cross section provides better information
than that done on the surface because the surface oxide and salt contamination are reduced. The
locations where EDX was performed are shown in Figure 8 while the results are presented in Figure 9.
Figure 7. Cross
The variation in the concentrations section SEM image (12,000×).
Figure 7.ofCross
nickelsection
and iron were
SEM unremarkable.
image (12,000×).Additionally, molybdenum
enrichment and surface chromium depletion were evident. The primary corrosion mechanism of
The cross section
stainless of the 100dissolution.
steel is chromium h stainlessAtsteel 316L
a depth sample6was
of roughly analyzed
microns, with
nominal EDX to characterize
composition was
The cross
observed.section
The of the
chromium 100 h stainless
dissolution to steel
the 316L
salt sample
occurred in was
two analyzed
reaction with
paths. EDX
First,
the key elements concentration. Performing EDX on the cross section provides better information theto characterize
reaction of the
key
thanelements
that doneconcentration. Performing
on the surface becauseEDX on the cross
the surface section
oxide provides
and salt better information
contamination than that
are reduced. The
done on the surface because the surface oxide and salt contamination are reduced. The locations
locations where EDX was performed are shown in Figure 8 while the results are presented in Figure where
9.
EDX was performed are shown in Figure 8 while the results are presented in Figure 9. The
The variation in the concentrations of nickel and iron were unremarkable. Additionally, molybdenum variation
in the concentrations
enrichment of nickel
and surface and iron
chromium were unremarkable.
depletion were evident.Additionally,
The primarymolybdenum enrichment
corrosion mechanism of
and
stainless steel is chromium dissolution. At a depth of roughly 6 microns, nominal compositionsteel
surface chromium depletion were evident. The primary corrosion mechanism of stainless was
is chromium
observed. Thedissolution. At a depthtoof
chromium dissolution theroughly 6 microns,
salt occurred in twonominal
reactioncomposition
paths. First, was observed.
the reaction of
Energies 2018, 11, 572 9 of 18

The chromium dissolution to the salt occurred in two reaction paths. First, the reaction of chromium
with oxidants from any remaining O2 or H2 O resulted in the formation of chromium oxide on the
surface Energies
which2018, dissolved
11, x into the molten salt. Second, the precipitation of chromium carbide 9 of 18 at the
grain boundaries dissolved
Energies 2018, 11, x into the molten salt. This molybdenum enrichment is in contrast
9 of 18 to the
chromium with oxidants from any remaining O2 or H2O resulted in the formation of chromium
near surface chromium reduction. At elevated temperature, high diffusion mobility of the chromium
oxide
chromium on the surface
with which
oxidants dissolved
from any into the molten
remaining O2 the
or H salt. Second, the precipitation of chromium
2O resulted in the formation of chromium
results in its depletion.
carbide at the grain
The vacancies
boundaries
resulted
dissolved
from
into the
chromium
molten salt.
depletion
This the
molybdenum
drive the molybdenum
enrichment is in
to
oxide on the surface which dissolved into the molten salt. Second, precipitation of chromium
the surface [48].
contrast Additionally,
to the
the near at elevated temperatures the migration of molybdenum to the grain
carbide at grainsurface
boundarieschromium reduction.
dissolved At molten
into the elevatedsalt.
temperature, high diffusion
This molybdenum mobility
enrichment is of
in
boundaries
the resulted in the information
its of
depletion. carbides.
contrast to the near surface chromium reduction. At elevated temperature, high diffusion mobilitythe
chromium results The vacancies resulted from the chromium depletion drive of
Themolybdenum
last
the area that
chromium toresults
the
was surface
examined [48]. Additionally,
wasThe
in its depletion. at elevated
thevacancies
weld zone. temperatures
In
resulted anfrom
effort
thetothe migration
avoid
chromium of molybdenum
introducing
depletion contaminants
drive the
into theto the grainelectron
sample,
molybdenum boundaries
to the surface resulted
beam [48]. in the formation
welding was used
Additionally, of carbides.
during
at elevated fabrication.
temperatures However,
the migration the composition,
of molybdenum
to theThe
microstructure,
lastboundaries
grain area that was
and properties
examined
resulted was
of theinmaterial
the the weld of
formation zone. In an effort to avoid introducing contaminants
carbides.
were changed by the welding process. Figure 10 shows
into the sample,
The oflastthe electron
areaweldthat was beam
examinedwelding
was100 was used
the weld during anfabrication.
zone. Insteel effort to avoidHowever, the composition,
introducing
a cross-section
microstructure, and zone
properties fromof the
the h
materialstainless
were changed 316L
by sample.
the welding few contaminants
Aprocess. micron
Figurethick
10 layer
into the sample, electron beam welding was used during fabrication. However, the composition,
can be seen
shows at the top
a cross-sectionof the image.
of the weld This layer was formed due to metal overflow from the fusion pool.
microstructure, and properties of zone from thewere
the material 100 h stainlessbysteel
changed the 316L sample.
welding A few
process. micron
Figure 10
A coatingthick
showsfrom
layer metal
can bevapor
a cross-section seen ofatdeposition
the
the top
weldof thecan
zone alsoThis
image.
from be 100
the seen
layer in
h was Figure
formed
stainless 10. The
due316L
steel vertical
to metal Alines
overflow
sample. seen
fewfrom theresulted
micron
from the fusion
rough pool.ion A coating
beam from
milling metal vapor
process deposition
during the can also be
preparation seen in
of Figure
the
thick layer can be seen at the top of the image. This layer was formed due to metal overflow from the 10.
sample. The vertical
Between lines
the upper
seen resulted
pool. A from
coatingthe rough
from metalion beam
vapor milling
deposition process
can alsoduring
layer and the base material, an interface layer was formed indicating that the fusion was incomplete.
fusion be seenthe
in preparation
Figure 10. Theof the sample.
vertical lines
Between
seen resulted the upperfrom layer
the and theionbase material, anprocess
interface layer the
waspreparation
formed indicating
of the that the
Additionally, micro-voids areroughpresent beam
both milling
along and adjacentduring
to the boundary. sample.
fusion
Betweenwasthe
incomplete. Additionally,
upper layer micro-voids
and the base material,are
anpresent both
interface along
layer andformed
was adjacentindicating
to the boundary.
that the
fusion was incomplete. Additionally, micro-voids are present both along and adjacent to the boundary.

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

(c) (d)
(c)over substrate cross section for EDX analysis:(d)
Figure 8. Selected locations (a) Sample location 1;
Figure 8.
(b) Selected
Sample locations
location over substrate
2; (c) Sample cross
location 3;cross
(d) section for 4.EDX analysis: (a) Sample location 1;
Sample
Figure 8. Selected locations over substrate section location
for EDX analysis: (a) Sample location 1;
(b) Sample location 2; (c) Sample location 3; (d) Sample location 4.
(b) Sample location 2; (c) Sample location 3; (d) Sample location 4.

Figure 9. EDX chemical analysis of SS 316L sample after 100 h heating.

Figure 9. EDX chemical analysis of SS 316L sample after 100 h heating.
Figure 9. EDX chemical analysis of SS 316L sample after 100 h heating.
Energies 2018, 11, 572 10 of 18
Energies 2018, 11, x 10 of 18

Figure 10. Cross-section SEM image of SS 316L sample in the weld zone after 100 h heating.
Figure 10. Cross-section SEM image of SS 316L sample in the weld zone after 100 h heating.

Three locations on the cross-section were chosen for EDX analysis. These areas were labeled as 1
for theThree locations
largest voidon atthe
thecross-section
center, 2 forwere thechosen for EDX analysis.
base material, and 3 for Thesetheareas
top were
layer,labeled as 1 for
respectively.
The results of the EDX analysis are listed in Table 6. At site 1, the presence of the salt is evidentofby
the largest void at the center, 2 for the base material, and 3 for the top layer, respectively. The results thea
EDX analysis are listed in Table 6. At site 1, the presence of the salt is evident by a
large fraction of sodium and chlorine present within the void area. It is possible that the salt could large fraction of sodium
and chlorine
have present
fallen into within
the void the void
from area. It during
the surface is possiblethethat
ion the saltmilling
beam could have fallenItinto
process. the void
is also fromthat
possible the
surface during the ion beam milling process. It is also possible that the void area
the void area was connected via a grain boundary or micro-crack to the surface in contact with the was connected via a grain
boundary
salt due toor micro-crack
the to the surface
melding process. in contact
Manganese with the
depletion wassalt due
also to the at
evident melding
all threeprocess.
sampleManganese
sites. This
further suggests that at high vapor pressure, the element evaporated during the weldingpressure,
depletion was also evident at all three sample sites. This further suggests that at high vapor process
the element
and evaporatedon
later redeposited during the welding
the surface during process and later redeposited on the surface during cooling.
cooling.

Table 6. EDX chemical analysis and resulting weight percentage of SS 316L sample in the weld zone,
Table 6. EDX chemical analysis and resulting weight percentage of SS 316L sample in the weld zone,
100 h testing.
100 h testing.

Sample Site O%
O% Cl%
Cl% Na%
Na% Fe%Fe% Cr%
Cr% Ni%
Ni% Mo%
Mo% Mn%
Mn%
11 1.7
1.7 20.5
20.5 10.5
10.5 50
50 15.2
15.2 9.6
9.6 1.6
1.6 0.5
0.5
22 1.1
1.1 -- -- 70.1
70.1 17.1
17.1 8.7
8.7 1.5
1.5 1.0
1.0
33 1.4
1.4 0.3
0.3 1.57
1.57 7171 11.24
11.24 9.1
9.1 33 0.7
0.7

Immediately after the stainless steel 316L sample was cut open, the color of the eutectic salt was
Immediately after the stainless steel 316L sample was cut open, the color of the eutectic salt was
visually inspected and its appearance was a pure white color. This also suggests that minimum
visually inspected and its appearance was a pure white color. This also suggests that minimum corrosion
corrosion had occurred. The color of a halide salt is sensitive to the level of chromium dissolution.
had occurred. The color of a halide salt is sensitive to the level of chromium dissolution. It has previously
It has previously been reported that salt discoloration from white to yellow can occur even after a
been reported that salt discoloration from white to yellow can occur even after a 100-h reaction of the
100-h reaction of the halide salt in a pre-baked stainless steel capsule [46]. To confirm the high
halide salt in a pre-baked stainless steel capsule [46]. To confirm the high sensitivity of the change in salt
sensitivity of the change in salt color, a simple re-melting test of the used NaF–NaCl eutectic salt
color, a simple re-melting test of the used NaF–NaCl eutectic salt mixture was conducted during which
mixture was conducted during which the top cap of the sample was removed leaving the interior of
the top cap of the sample was removed leaving the interior of the stainless steel 316L sample and the salt
the stainless steel 316L sample and the salt exposed to the ambient environment. When the container
exposed to the ambient environment. When the container was not sealed, the color of the eutectic salt
was not sealed, the color of the eutectic salt changed from pure white to a light yellow after only one
changed from pure white to a light yellow after only one cycle of solidification and re-melting.
cycle of solidification and re-melting.
4.2. SS 316L, 2500 H
4.2. SS 316L, 2500 H
Figure 11 shows that surface morphology of a sample after 2500 h of heating. The results indicate
that aFigure 11 metal
uniform showsdissolution
that surface morphology
process occurredofatasome
sample after
point 2500
after the hinitial
of heating. The results
100 h. While there
indicate that a uniform metal dissolution process occurred at some point after the initial
were no signs that profound intergranular corrosion occurred, more pits presented at the junctions 100 h. While
of
there were no signs that profound intergranular corrosion occurred, more pits presented
grain boundary while shallow pits were observed within the grains themselves. Preferential dissolution at the
junctions of grain
occurred along boundary
certain while shallow
crystal orientations as somepits
grainwere
facetsobserved within
were exposed. Thethe grains
noted themselves.
characterizations
Preferential dissolution occurred along certain crystal orientations as some
suggest that a change in the corrosion mechanism occurred between 100 and 2500 h’ exposure with grain facets were
the
exposed. The noted characterizations suggest that a change in the corrosion mechanism
molten salt. The corrosion became uniform on a macro-scale after an initial intergranular boundary attack. occurred
between 100 and 2500 h’ exposure with the molten salt. The corrosion became uniform on a
macro-scale after an initial intergranular boundary attack.
Energies 2018, 11, 572 11 of 18
Energies 2018, 11, x 11 of 18

Energies 2018, 11, x 11 of 18

(a) (b)
Figure 11. (a) Top-down and (b) 20°◦tilted SEM images of SS 316L sample surface, 2500 h testing (5000×).
Figure 11. (a) Top-down and (b) surface, 2500 h testing (5000×).
(a)20 tilted SEM images of SS 316L sample(b)
The conclusions that no and
Figure 11. (a) Top-down intergranular penetration
(b) 20° tilted SEM images of SSoccurred
316L sample can be substantiated
surface, by examining
2500 h testing (5000×).
The conclusions
the increased resolutionthatimage
no intergranular penetrationarea
of the cross-sectional occurred
showncan in be substantiated
Figure 12a. Instead by examining
of the top
the increased resolution
The conclusions
down surface EDX analysis image
thatthat of the cross-sectional
no intergranular
was done onpenetration area shown in
occurredacan
the 100 h sample, Figure
more 12a. Instead
be substantiated of the topsurvey
by examining
accurate cross-section down
surface
was theEDX
performed.analysis
increasedThe that was
resolution
results image
are done of on
the the
presented in 100 h sample,
cross-sectional
Figure 12b.area
Theashown
more accurate
in cross-section
Figure 12a.
concentrations of theInstead of survey was
the topwere
key elements
down surface
performed. The EDX analysis
results are that was done
presented in on the12b.
Figure 100 hThe
sample, a more accurate
concentrations of cross-section
the key surveywere
elements
compared to those seen in the 100 h samples. The variation in the concentration of the key elements
was performed.
compared to thosedepthThe results
seen inisthe are presented in Figure 12b. The concentrations of the key elements were
with the sample’s less100
sinceh samples.
the elementsThe variation in thetime
had sufficient concentration
to migrateoftothe keyrespective
their elements
with compared
the sample’sto those seen in the
depth is less since 100 h samples. The variation in the concentration of the key elements
equilibrium
with theconcentrations
sample’s depthwithin thethe
is less since
elements had sufficient time to migrate to their respective
material.
the elements had sufficient time to migrate to their respective
equilibrium concentrations within the material.
equilibrium concentrations within the material.

(a) (a) (b)

(b)

FigureFigure
12. (a)12.Cross
(a) Cross section
section SEMSEM image(10,000×)
image (10,000×)and
and (b) EDX
EDXchemical
chemicalanalysis of SS
analysis of 316L sample
SS 316L sample
Figureafter (a) Cross
12. 2500 h
section SEM image (10,000×) and (b) EDX chemical analysis of SS 316L sample
heating.
after 2500 h heating.
after 2500 h heating.
As with the 100 h sample, the weld zone cross section was also analyzed via SEM. Unlike in the
As with the 100 h sample, the weld zone cross section was also analyzed via SEM. Unlike in the
100with
h heated sample, the distinct fusion pool layer and micro-voids in the weld zone Unlike
were not
100 hAsheated the 100
sample, h sample, the weld
the distinct fusion zone
poolcross section
layer and was also analyzed
micro-voids in thevia SEM.
weld zone were in not
the
present in the 2500 h sample. The exact cause for this is unknown. A plausible explanation is that
100 h heated
present in thesample,
2500 hthe distinct
sample. fusion
The exact pool layer
cause forand micro-voids
thisthe
is fusion
unknown. in A
theplausible
weld zone were not present
explanation is that
corrosion occurred at the interface boundary between pool and the base metal layers. This
in the 2500
corrosion h sample.
occurred at The
the exact cause
interface for
boundary this is unknown.
between the A plausible
fusion pool andexplanation
the base is that
metal corrosion
layers. This
would allow the thin fusion pool layer to delaminate from the material surface.
occurred
would at the
allow theinterface
thin fusionboundary between
pool layer the fusion
to delaminate frompool
theand the base
material metal layers. This would
surface.
allow4.3.
theInconel
thin fusion pool
625, 100 H layer to delaminate from the material surface.
4.3. InconelAs625, 100
with Hstainless steel 316L samples, an untested Inconel 625 sample was examined as a
the
4.3. Inconel 625, 100 H
baseline
As for comparison.
with the stainless steelSimilar
316Ltosamples,
the resultsanofuntested
the stainless steel625
Inconel 316L sample,was
sample the examined
cold work as a
As with the grain
stainless steel 316L samples, anasuntested Inconel 625 sample was examined as a baseline
baseline for comparison. Similar to the results of the stainless steel 316L sample, the images
introduced refinement and distortion well as machining marks being visible in both cold work
for comparison.
of Figure 13.Similar to the
However, results
unlike withofthe
thestainless
stainless steel
steel 316L
316L, thesample, the cold
EDX analysis work
results introduced
showed that nograin
introduced grain refinement and distortion as well as machining marks being visible in both images
surface
refinement elements
and deviated
distortion as wellfrom the nominal
as machining composition
marks of the
being visible bulk images
in both alloy. Although
of Figurethe 13. same
However,
of Figure 13. However, unlike with the stainless steel 316L, the EDX analysis results showed that no
equipment and process parameters were used for the electron beam welding of both
unlike with the stainless steel 316L, the EDX analysis results showed that no surface elements deviated the Inconel 625
surfaceandelements
stainless deviated
steel 316L from the manganese
containers, nominal composition
and copper of the thin
enriched bulkfilm
alloy.
were Although
not found thethesame
in
from the nominal composition of the bulk alloy. Although the same equipment and process parameters
equipment
Inconeland process
sample. parameters
Inconel were used
625 has elements for the
of a low electron
vapor beam
pressure welding
and high meltingof both the Inconel
temperature. The 625
were used for the electron beam welding of both the Inconel 625 and stainless steel 316L containers,
and stainless
manganese steel
and316L containers,
copper content ofmanganese and copper
Inconel are 0.03% enriched
and 0.02% thin film
respectively. Thesewere
levelsnotarefound in the
at least
Inconel sample. Inconel 625 has elements of a low vapor pressure and high melting temperature. The
manganese and copper content of Inconel are 0.03% and 0.02% respectively. These levels are at least
Energies 2018, 11, 572 12 of 18

manganese and copper enriched thin film were not found in the Inconel sample. Inconel 625 has elements
of a low vapor pressure and high melting temperature. The manganese and copper content of Inconel are
0.03% and 0.02% respectively. These levels are at least an order of magnitude lower than that of stainless
steel 316L,Energies
thus during
2018, 11, x the welding process, there were insufficient elements with high vapor 12 of 18pressure to
Energies 2018, 11, x 12 of 18
evaporate and then redeposit during cooling. The chemical composition of the Inconel 625 surface after
an order of magnitude
Energies 2018, 11, x lower than that of stainless steel 316L, thus during the welding process, there
12 of 18
the weldingan process is shownlower
order of magnitude in Table
than 7.
that of stainless steel 316L, thus during the welding process, there
were insufficient elements with high vapor pressure to evaporate and then redeposit during cooling.
were insufficient
Comparing to elements with high vapor pressure to evaporate and then redeposit during cooling.
The
an order of the
chemical stainless
composition
magnitude lowersteel
of the 316L
that ofsample,
thanInconel 625 the
surface
stainless images
after
steel of
the welding
316L, thus the Inconel
process
during 625
is shown
the welding sample surface were
in Tablethere
process, 7.
The chemical composition of the Inconel 625 surface after the welding process is shown in Table 7.
significantly
weredifferent
Comparing
insufficient after
to 100 hwith
the
elements of heating.
stainless high vaporThe
steel 316L surface
sample,
pressurethe of the Inconel
images
to evaporateof and then625
the Inconel 625 sample
sample
redeposit wascooling.
surface
during covered evenly
were
Comparing to the stainless steel 316L sample, the images of the Inconel 625 sample surface were
significantly
The
by both salt chemicaland
residues different
composition afterof
oxide. 100
the hInconel
Ultrasonic of heating.
agitationThe surface
625 surface of welding
the Inconel
afteremployed
was the 625 issample
process
to clean shown
the was covered
in Table
sample in7.a de-ionized
significantly different after 100 h of heating. The surface of the Inconel 625 sample was covered
evenly by both salt
Comparing residues
to the andsteel
stainless oxide. Ultrasonic
316L agitation
sample, the imageswas employed
of the to clean
Inconel 625 thesurface
sample samplewere
in a
water bathde-ionized
to aid
evenly by in
both the saltevaluation
residues andof theUltrasonic
oxide. samples. The
agitation sample
was employedsurface afterafter
to clean cleaning
the sample inisa shown in
significantlywater bath after
different to aid100in the
h ofevaluation
heating. Theof the samples.
surface of theTheInconel
sample625 surface
sample wascleaning
covered is
de-ionized
Figure 14. shown
A 0.5 by water
thick bath to aid in the
oxide evaluation of the samples. The sample surface15.
after cleaning is
evenly µm
in Figure
both salt14. A 0.5layer
residues µm uniformly
and thick
oxide.oxide
Ultrasoniccovered
layer uniformly
agitationthe
was surface,
covered
employed Figure
the surface, The
Figure
to clean the formation
15. The
sample in a of the
shown in Figure 14. A 0.5 µm thick oxide layer uniformly covered the surface, Figure 15. The
oxide layer starts as
formation
de-ionized of athegrain
water oxideto
bath with
layer
aid inthe
thesize
starts as of a few
a grain
evaluation hundred
with
of the nm
the sizeThe
samples. aand
few then
of sample hundred
surfaceagglomerates
nmcleaning
after and then isand forms
formation of the oxide layer starts as a grain with the size of a few hundred nm and then
agglomerates
shown
a dense layer. in Figure
However, andgaps
forms
14. a dense
A 0.5 µm layer.among
thick However,
oxide layergaps are present
uniformly among
covered the the grains
surface, which15.
Figure permit
The
agglomerates and formsare present
a dense layer. However, the grains
gaps which
are present permit
among thethe molten
grains which salt
permit intrusion.
the molten of
formation saltthe
intrusion.
oxide layer starts as a grain with the size of a few hundred nm and then
the molten salt intrusion.
agglomerates and forms a dense layer. However, gaps are present among the grains which permit
the molten salt intrusion.

(a) (b)
(a) (b)
Figure 13. (a) Top down and (b) cross sectional SEM images of Inconel 625 sample surface, prior to
Figure
Top13.down
(a) Top
(a) (5000×).
Figure 13.test and (a) cross
down
(b) and (b) cross sectional
sectional SEM images
SEM images of Inconel
of Inconel 625 (b)
625 samplesample surface,
surface, prior
prior toto
test (5000×).
test (5000×).
Figure 13. (a) Top down and (b) cross sectional SEM images of Inconel 625 sample surface, prior to
test (5000×).

Figure 14. Top-down SEM image of Inconel 625 sample surface after 100 h heating (5000×).
Figure 14. Top-down SEM image of Inconel 625 sample surface after 100 h heating (5000×).
Figure 14. Top-down SEM image of Inconel 625 sample surface after 100 h heating (5000×).
Figure 14. Top-down SEM image of Inconel 625 sample surface after 100 h heating (5000×).

Figure 15. SEM image of oxide complex formed on the Inconel 625 surface. The top layer is shown on
Figure 15. SEM image of oxide complex formed on the Inconel 625 surface. The top layer is shown on
Image is a carbon coat protection layer for the ion milling process (20,000×).
Image is a carbon coat protection layer for the ion milling process (20,000×).
Figure 15. SEM image of oxide complex formed on the Inconel 625 surface. The top layer is shown on
Figure SEM isimage
15. Image of coat
a carbon oxide complex
protection formed
layer onmilling
for the ion the Inconel
process 625 surface. The top layer is shown
(20,000×). on
Image is a carbon coat protection layer for the ion milling process (20,000×).
Energies 2018, 11, 572 13 of 18

Table 7. Chemical composition at Inconel 625 surface after machining and EB welding, untested.

Sample Material O% Fe% Cr% Ni% Mo% Nb% Al%

Energies 2018, 11, x Inconel 625 0.47 1.6 20.7 65.4 8.4 3.2 0.3 13 of 18

Table 7. Chemical composition at Inconel 625 surface after machining and EB welding, untested.
The oxide complex that forms on the surface of the Inconel 625 sample is stable and resistant to
dissolution, unlike the Sample Material
oxide that formsO%in theFe% Cr% steel
stainless Ni%316 Mo% Nb% which
L samples Al% is easily dissolved in
the molten salt. An EDX analysis of the surface was conducted on a single0.3location and the results
Inconel 625 0.47 1.6 20.7 65.4 8.4 3.2

are listed in Table 8. Note that the values in Table 8 are listed in atomic percentage. The exact oxide
The oxide complex that forms on the surface of the Inconel 625 sample is stable and resistant to
coulddissolution,
not be determined basedthat
unlike the oxide on forms
the EDX analysis
in the stainlessalone, however,
steel 316 L samplesthewhich
oxideisiseasily
rich dissolved
in nickel and
chromium. The extremely
in the molten lowanalysis
salt. An EDX Na andofMo thecontents
surface wasindicate minimal
conducted on ainteraction with
single location andboth
the the salt and
results
the alloy substrate.
are listed in Table 8. Note that the values in Table 8 are listed in atomic percentage. The exact oxide
could not be determined based on the EDX analysis alone, however, the oxide is rich in nickel and
chromium.Table 8. The atomic
The extremely lowpercentage
Na and Mo ofcontents
Inconel 625 sample
indicate surfaceinteraction
minimal after 100 h with
testing.
both the salt
and the alloy substrate.
Element Cr O Ni Mo Fe Na
Table 8. The atomic percentage of Inconel 625 sample surface after 100 h testing.
Atomic% 49 31 21.5 1.5 0.6 0.25
Element Cr O Ni Mo Fe Na
Atomic% 49 31 21.5 1.5 0.6 0.25
A view of the microstructure of the Inconel 615 sample’s cross-section can be seen in Figure 16.
The grainsAalong
view ofthe
thetop surface are much
microstructure smaller615
of the Inconel than those seen
sample’s deeper in
cross-section canthe
be sample. Additionally,
seen in Figure 16.
recrystallization formed
The grains along theannealing
top surfacetwins were found
are much smallerinthan
the those
large grains.
seen deeperAfterin100
the hsample.
of heating,
Additionally,
it appears that therecrystallization
majority of the formed
grainsannealing twins wererecrystallization.
have undergone found in the large grains. After 100 h of of
The recrystallization
heating, it appears that the majority of the grains have undergone
grains reduces grain boundary migration mobility. Low grain boundary mobility decreases recrystallization. The both
recrystallization of grains reduces grain boundary migration mobility. Low grain boundary
growth and recrystallization in the annealing process. Furthermore, when carbides are formed on mobility
graindecreases
boundaries both growth and recrystallization in the annealing process. Furthermore, when carbides
they have a pinning or retarding effect on the mobility of the grain boundary and
are formed on grain boundaries they have a pinning or retarding effect on the mobility of the grain
therefore slows down the recrystallization and the growth [49].
boundary and therefore slows down the recrystallization and the growth [49].

Figure 16. Cross-sectional SEM image of Inconel 625 sample after 100 h heating (10,000×).
Figure 16. Cross-sectional SEM image of Inconel 625 sample after 100 h heating (10,000×).
A total of four sites were selected for the EDX analysis on the cross-section. The first site, site 1,
was
A chosen
total in thesites
of four oxidewere
layer.selected
Sites 2 and
for3 were picked
the EDX at grain on
analysis boundaries and precipitates.
the cross-section. TheSite 4 site,
first
site 1,was
wasselected
chosenwithin
in thethe sample
oxide baseSites
layer. material.
2 andThe results
3 were of EDX
picked atanalysis are tabulated
grain boundaries in Table
and 9.
precipitates.
Site 4The
wassurface
selectedanalysis results from site 1 further substantiate the presence of a chromium enriched
within the sample base material. The results of EDX analysis are tabulated in Table 9.
oxide. Aluminum oxide precipitates are present based on the results from sites 2 and 3. As expected
The surface analysis results from site 1 further substantiate the presence of a chromium enriched oxide.
the results from site 4 are comparable to the untested baseline composition. Note that sodium from
Aluminum oxide precipitates are present based on the results from sites 2 and 3. As expected the
the eutectic salt was not observed in any of the four selected sites.
results from site 4 are comparable to the untested baseline composition. Note that sodium from the
eutectic salt was not 9.observed
Table The weightinpercentage
any of the four selected
of Inconel sites.
625 sample cross section after 100 h heating.

Sample Site Cr% Ni% O% Mo% Fe% Al% Mn% Na% Cl%
1 53.2 31.7 12.9 2.8 1 - - - -
2 18 67.9 3.9 4.4 1.7 4.4 0.1 - -
3 18.6 68 3.7 4.6 1.7 3.1 0.16 - 0.2
4 18.2 74.6 0.35 5.1 1.7 - 0.1 - -
Energies 2018, 11, 572 14 of 18

Table 9. The weight percentage of Inconel 625 sample cross section after 100 h heating.

Sample Site Cr% Ni% O% Mo% Fe% Al% Mn% Na% Cl%
1 53.2 31.7 12.9 2.8 1 - - - -
2 18 67.9 3.9 4.4 1.7 4.4 0.1 - -
3 18.6 68 3.7 4.6 1.7 3.1 0.16 - 0.2
4 18.2 74.6 0.35 5.1 1.7 - 0.1 - -
Energies 2018, 11, x 14 of 18

4.4. Inconel 625,

4.4. Inconel 625, 2500
2500 H
H
As
As with
with the
the 100
100 hh sample,
sample, thethe Inconel sample was
Inconel sample was analyzed after 2500
analyzed after 2500 hh exposure
exposure to to the
the molten
molten
salt. The Inconel 625 was also cleaned to remove any salt residue before conducting
salt. The Inconel 625 was also cleaned to remove any salt residue before conducting the SEM analysis. the SEM analysis.
A
A surface
surface morphology
morphology that that was
was highly similar to
highly similar to that
that observed
observed in in the
the 100
100 h
h sample
sample waswas seen
seen in
in the
the
2500
2500 h sample, Figure 17. The oxide layer with porous polycrystalline was still seen, but the grain
h sample, Figure 17. The oxide layer with porous polycrystalline was still seen, but the grain
size
size of
of the layer and
the layer and the
the thickness
thickness remained
remained unchanged.
unchanged. TheseThese results
results indicate
indicate that
that the
the formed
formed oxide
oxide
complex
complex is resistant to container material dissolution into the eutectic mixture of NaCl–NaF usedthe
is resistant to container material dissolution into the eutectic mixture of NaCl–NaF used in in
experiments. The porous oxide layer after 2500 h is a result of extremely slow solid-state
the experiments. The porous oxide layer after 2500 h is a result of extremely slow solid-state inter-granular
diffusion of thediffusion
inter-granular oxide under the test
of the conditions.
oxide under theThe temperatures
test conditions. present in the experiment
The temperatures presentwere far
in the
below the melting point of the normal oxide.
experiment were far below the melting point of the normal oxide.

Figure 17. Top-down SEM image of Inconel 625 sample surface after 2500 h heating (10,000×).
Figure 17. Top-down SEM image of Inconel 625 sample surface after 2500 h heating (10,000×).

The results of a cross sections SEM analysis further validate the findings obtained from the
Theanalysis,
surface results ofFigure
a cross18.
sections SEM analysis
The measured further
thickness validate
of the oxidethe findings
layer and the obtained
size of from the surface
the grains show
analysis, Figure 18. The measured thickness of the oxide layer and the size
little change with the testing time. It was also observed that there was no apparent corrosion of the grains show little
change with the testing time. It was also observed that there was no
between the alloy surface and the oxide layer. Furthermore, there was minimal intergranularapparent corrosion between
the alloy surface
boundary stack and the oxide
activity layer.
present. A Furthermore,
previous study there was minimal
reported intergranulargrain
that inter-granular boundary stack
boundary
activity present. A previous study reported that inter-granular grain boundary
corrosion was the primary corrosion mechanism of nickel alloys in alkali halide molten salt systems corrosion was the
primary corrosion mechanism of nickel alloys in alkali halide molten salt systems
[50]. Contrary to the previous report, no significant inter-granular penetration was observed in any [50]. Contrary to
the previous
of the samples report, no significant
examined. A few microninter-granular
or sub-micronpenetration was observed
sized voids were seen. in These
any ofare thelikely
samplesthe
examined. A few micron or sub-micron sized voids were seen. These are likely
result of corrosion resulting from material defects in the manufacturing process. Given the minimal the result of corrosion
resulting
change offrom material
the oxide defects in the
morphology, themanufacturing process.and
lack of oxide growth Giventhe the minimal
clear interfacechange
presentof the oxide
between
morphology,
the oxide and thethe
lack of oxide
Inconel 625growth
alloy and the clear
surface interface
strongly present
supports thebetween
conclusionthe oxide and the
that, after theInconel
initial
625 alloy surface strongly supports the conclusion that, after
stage, the corrosion rate in the Inconel system has been greatly reduced. the initial stage, the corrosion rate in the
Inconel system has been greatly reduced.
[50]. Contrary to the previous report, no significant inter-granular penetration was observed in any
of the samples examined. A few micron or sub-micron sized voids were seen. These are likely the
result of corrosion resulting from material defects in the manufacturing process. Given the minimal
change of the oxide morphology, the lack of oxide growth and the clear interface present between
the oxide
Energies 2018,and the Inconel 625 alloy surface strongly supports the conclusion that, after the 15
11, 572 initial
of 18
stage, the corrosion rate in the Inconel system has been greatly reduced.

Figure 18. Cross-section SEM image of Inconel 625 sample after 2500 h heating (10,000×).
Figure 18. Cross-section SEM image of Inconel 625 sample after 2500 h heating (10,000×).

Figure 18 shows where the four sites for EDX analysis were chosen. As shown on the upper left
corner of Figure 18, site 1 was inside the void. The other sites were located successively deeper into
the depth of the cross-section towards the base alloy material. The results of the EDX analysis are
listed in Table 10. The results are mostly comparable to the composition of the base alloy elements.
The composition was fairly uniform across the sample with the exception of the indication of an oxide
precipitate at site 2. The results from site 1 show that molten salt was able to penetrate into the void
space through a grain boundary.

Table 10. The weight percentage of Inconel 625 sample cross section after 2500 h heating.

Sample Site Ni% Cr% Fe% Mo% Nb% O% Na% Cl%

1 64.6 19.1 1.4 2.4 0.4 0.43 7 3.7
2 72.7 18.4 1.5 5.6 1.2 30.57 - -
3 71.5 20.7 1.3 5.2 1.2 3.7 - 0.2
4 71 19.1 1.4 5.1 1.2 0.35 - -

5. Conclusions
The compatibility of stainless steel 316L and Inconel 625 to NaCl–NaF eutectic mixture was studied
to determine the suitability for use in a latent heat TES system. A small amount of corrosion was
present in both container materials after 100 h of high-temperature heating. However, neither sample
suffered significant damage after 2500 h of high-temperature heating. The undesirable inter-granular
grain boundary attack found in SS316L samples is in the order of 1–2 µm in depth. On the surface
of the Inconel 625 sample, an oxide complex formed. This oxide complex is resistant to container
material dissolution into the molten salt. After 2500 h of high-temperature exposure, the surface
morphology of both stainless steel 316L and Inconel 625 remained largely unchanged, but the corrosion
process switched from an initially localized pattern to a more uniform pattern. After 2500 h of
high-temperature heating, the measured corrosion depth of Inconel 625 remained roughly 1–2 µm,
indicating the deceleration of corrosion rate. Both Inconel 625 and stainless steel 316L demonstrated
good compatibility with the chosen eutectic mixture of NaF–NaCl in a system that has been sealed
and the excess water and oxygen inside the container has been removed. The low corrosion activity
in Inconel 625 samples shows an advantage over the stainless steel 316L for long term operation.
Therefore, the results can also provide good insight on the selection of the material for use in a TES
system that utilizes a NaF–NaCl eutectic as PCM.
Energies 2018, 11, 572 16 of 18

Acknowledgments: This work was supported by DOE EERE under the grant DE-FC36-08GO18157. The authors
would like to thank Bruce Arey at Environmental Molecular Sciences Laboratory at Pacific Northwest National
Laboratory (PNNL) and Brian Iverson at Sandia National Laboratory for technical support.
Author Contributions: Songgang Qiu served as the principal Investigator for the research project. He conceived
and performed the analytical analysis. Ming Fan designed and performed experimental testing. Songgang Qiu,
Ming Fan, and Laura Solomon analyzed the data and wrote the paper.
Conflicts of Interest: The authors declare no conflict of interest.

Abbreviations
CSP Concentrating Solar Power
EDX Energy-Dispersive X-ray Spectroscopy
PCM Phase Change Material
SEM Scanning Electron Microscopy
TES Thermal Energy Storage
EDX Energy Dispersive X-ray Spectroscopy

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