Article

Anodic Protection Assessment Using Alumina-

Forming Alloys in Chloride Molten Salt for
CSP Plants
Angel G. Fernández and Luisa F. Cabeza *
GREiA Research Group, Universitat de Lleida, Pere de Cabrera s/n, 25001 Lleida, Spain;
[email protected]
* Correspondence: [email protected]

Received: 8 December 2019; Accepted: 29 January 2020; Published: 4 February 2020

Abstract: The generation of a natural protective coating in alumina-forming alloys was analyzed
using a ternary chloride molten salt as a thermal energy storage material for concentrated solar
power (CSP) technology. The formation of the protective layer was monitored using electrochemical
impedance spectroscopy (EIS). A protective layer model for the OCT alloy and a localized corrosion
model for the OCI and OC4 alloys were obtained after 5 h of immersion. The corrosion rates
calculated using the linear polarization technique (LPR), were 8.03, 21.55, and 7.61 mm/year for
OC4, OCI, and OCT alloys, respectively. These results were confirmed by scanning electron
microscopy and X-ray diffraction. Our analysis showed that MgAl2O4 was the main protective
coating generated by the alumina-forming alloys.

Keywords: concentrated solar power; thermal energy storage; corrosion mitigation; chloride molten
salt; alumina-forming alloys; anodic protection

1. Introduction
In the last years, an opportunity to obtain higher power generation efficiencies has been
identified by integrating the supercritical CO2 (sCO2) Brayton power cycle. To achieve this
integration, storage temperatures in concentrated solar power (CSP) plants must be high (up 550 °C).
In order to raise the storage temperature, a molten salt with suitable chemistry is needed. Some of
the main challenges of using high-temperature molten salts are that they must be compatible with
the commercial alloys that will be in contact with the storage materials and that alloy requirements
and costs should be balanced [1].
Due to their low cost and high decomposition temperature, molten chlorides are considered to
be good candidates. The high operation temperatures require the study of corrosion mitigation
strategies to reduce the corrosion rate of the containment materials to around 20 µm/year, since their
life cycle needs to be at least of 30 years [2–4]. One of the corrosion mitigation strategies is thermal
purification development in chloride salt before the start of the corrosion process. This approach,
previously analyzed by Fernandez and Cabeza [5], achieved a corrosion rate reduction of around
68%.
On the other hand, the use of coatings as protective barriers on the surface of steel is a second
possibility, although it could increase the system’s cost. For example, the use of alumina-forming
alloys has been studied, since alumina scales (generated on the surface of steel) were reported to be
more protective than chromia scales, which usually form on conventional stainless steel [6].
The generation of anodic protection layers in chloride molten salts has been developed by
different authors. Indacochea et al. [7] analyzed the corrosion resistance of several ferrous alloys and

Coatings 2020, 10, 138; doi:10.3390/coatings10020138 www.mdpi.com/journal/coatings

Coatings 2020, 10, 138 2 of 12

tantalum specimens in lithium chloride salt, obtaining higher corrosion resistance under reducing
conditions.
A second approach to achieve corrosion mitigation consists in the addition of a sacrificial anode
to the molten salt. Garcia-Diaz [8] and Ding [9] reported a reduction of the corrosion rates when a
metal of Mg in a chloride molten salt was used as cathodic protection. Specifically, the addition of
1.15 wt.% of Mg reduced the corrosion rate of Haynes 230 at 850 °C by 35 times, reaching a value of
less than 15 µm/year, when compared to the baseline rate measured without the addition of Mg. A
key consequence of this effect was the deposition of MgO on the cathode, which led to the passivation
of this electrode, causing a significant reduction of the electrolysis current [9]. These strategies for
corrosion mitigation were also summarized in a recent review by Ding et al. [10].
In summary, the aim of this paper was to analyze the corrosion resistance of different alumina-
forming alloys in contact with a ternary chloride molten salt, proposed as an anodic protection
strategy.

2. Anodic Protection in Chloride Molten Salts

Anodic protection is a corrosion mitigation strategy that controls the corrosion rate of the surface
to be protected by making it the anode of an electrochemical cell. The initial reaction of the anode is
usually accompanied by surface passivation which hinders the reaction and, hence, corrosion. Before
applying these anodic protection strategies, some purification treatments in chloride molten salts,
aiming to reduce corrosive impurities, have been suggested [4]. One of the most studied mixtures
consisted of MgCl2-NaCl-KCl (60-20-20 mol%), which has a melting point of ~400 °C and a thermal
stability up to 800 °C. Water molecules in MgCl2 (hexahydrate) need to be removed, since MgOHCl
was identified by some authors [11–14] as the main corrosive impurity that is formed through the
following reaction at ~167 °C [15]:
MgCl2 * 2H2O  MgOHCl + HCl + H2O
The dehydration of the monohydrate occurs at ~235 °C and also produces MgOHCl:
MgCl2 * H2O  MgOHCl + HCl
Ding et al. reported a thermal decomposition of MgOHCl between ~415 °C and ~555 °C [16]
producing MgO and HCl:
MgOHCl MgO + HCl
The strategy of using coatings as anodic protection has been proposed recently, especially for specific
components inside the CSP plant, i.e., turbine blades [17]. Coatings could be a suitable option in order
to decrease corrosive attacks by molten salts and to reduce the cost of container materials used in
storage tanks and pipelines. Some coatings tested in the literature are composed of MCrAlX (M: Ni,
and/or Co; X: Y, Hf, Si, and/or Ta) [17] and form an adherent alumina layer on the alloy surface
providing high-temperature corrosion resistance in chloride molten salt.
The resistance of aluminum coatings as slurries or alumina-forming alloys has been widely
tested, resulting acceptable in harsh environments. Audigie et al. [18] evaluated the corrosion
resistance of an Al coating slurry immersed in 60% NaNO3 + 40% KNO3 molten salt at 580 °C,
obtaining a better resistance compared with that of uncoated steel (P92).
These results have raised a significant interest in alumina-forming alloys (AFAs) as storage
container material with good corrosion-resistance. AFAs, consisting of alumina protective layers,
have been proposed as substitutes of chromia layers, which has been normally formed in commercial
stainless steel [19,20].
Gomez-Vidal evaluated AFAs exposed to molten MgCl2 – 64.41 wt.% KCl at 700 °C in a flowing
Ar atmosphere [2]. In this research, Inconel 702 (IN702), Haynes 224 (HR224), and Kanthal APMT
(APMT) were pre-oxidized at different temperatures, for different dwelling times, and in different
atmospheres to produce the protective layers. Electrochemical tests and conventional long-term tests
Coatings 2020, 10, 138 3 of 12

based on weight changes were both used to down-select the best-performing alloy and surface pre-
oxidation conditions.
Linear sweep voltammetry (LSV) measurement and sample characterization showed that the
IN702 alloy presented the best corrosion-resistant properties due to the formation of a stable α-Al2O3
coating. It is important to highlight that this alloy was pre-oxidized in zero air (ZA) at 1050 °C for 4
h. On the other hand, another pre-oxidation method was carried out with this alloy, using Ar instead
ZA, forming α-(Al0.9Cr0.1)2O3. This coating showed reduced protective properties due to the presence
of the less stable Cr. Since this pre-oxidation process would increase the material’s cost, in this
research, alumina-forming alloys are proposed as a protective coating in the corrosive environment
of the operation conditions.

3. Materials and Methods

The molten salt tested was a eutectic mixture composed of 20.4 wt.% KCl + 55.1 wt.% MgCl2 +
24.5 wt.% NaCl (Sigma Aldrich, St. Louis, MO, USA, with 99% purity), at 720 °C under inert
atmosphere (N2).
Three electrodes, composed of a working electrode (WE, alloy tested 10x10x2 mm), a reference
electrode (RE, Pt wire), and a counter electrode (CE, Pt mesh), were used. The lectrodes were
immersed in the molten salt, acting as an electrolyte, and the open circuit potential (OCP) was
measured using a potentiostat (Gamry 1010E, Gamry, Warminster, PA, USA). The experimental
apparatus is shown in Figure 1.

Figure 1. Experimental apparatus designed for corrosion tests in controlled atmosphere. 1: furnace, 2:
molten salt reactor, 3: counter electrode, 4: thermocouple, 5: working electrode, 6: reference electrode,
7: gas inlet, 9: molten salt, 10: carrier gas, 8: off-gas system (which consisted of 11: MgO trap for
chlorine, 12: moisture removal, 13: 1 M NaOH scrubber to neutralize H+, and 14: gas exhaust).

Electrochemical impedance spectroscopy tests were carried out after 1, 3, and 5 h of immersion
to monitor the corrosion mechanism. After 8 h of immersion, linear polarization resistance tests were
performed from a potential of -0.6 to 0.4 V, using a scanning range of 0.005 V/s (0.00244 V at each
step).
Coatings 2020, 10, 138 4 of 12

Thermal treatment was performed as previously reported [5], in order to reduce the corrosive
impurities present in commercial chloride molten salts, especially in MgCl2, following different
isothermal steps (according to the vapor–pressure curve of hydrated MgCl2) and dwelling times: 70
°C (2 h) – 117 °C (2 h) – 145 °C (4 h)- 190 °C (4 h) – 227 °C (4 h) – 300 °C (4 h) – 450 °C (3 h) – 600 °C (1
h) – 720 +C.
The chemical composition of the commercial salt used in this research are shown in Table 1.

Table 1. Chemical composition of the ternary chloride salt tested.

K (%) Mg (%) Na (%) Mn (ppm) SO4 (ppm) Cl (%) H2O (%)

20.6 11.9 3.4 1.8 162 60 5

The use of an inert atmosphere (N2) is key to avoid a catastrophic corrosion caused by contact with
the chloride molten salts. Also, it is important to highlight the formation of the alumina protective
layers in the tested alloy with low oxygen content in the molten salt (Table 1).
Anodic protection tests were carried out after thermal purification in three different alloys,
whose chemical composition is shown in Table 2.
Electrochemical techniques were used to monitor the corrosion mechanism in the tested
materials. For this purpose, an electrochemical impedance test was carried out using equivalent
circuits on the basis of the corrosion mechanism model of the Randles circuit [21].
Nyquist plots were used to represent the real part of the impedance on the abscissa axis and the
imaginary part on the ordinate axis, both at different frequencies [22]. The obtained semicircle
represented the total impedance (Z) of the Randles circuit, given by Equation (1):
𝟏
𝒁 = 𝑹𝑺 +
𝟏 (1)
+ 𝒋𝝎𝑪𝒅𝒍
𝑹𝒄𝒕
where Rs is the resistance of the solution, Rct is the resistance to charge transfer, 𝑗𝜔 is the imaginary
radial frequency, and Cdl is the capacitance of the double layer.

Table 2. Chemical composition of the tested alloys.

wt.%
Alloy
Zr Mn Cr Nb Cu Ti Ni Al Mo Fe
OC4 - - 14 2.5 0.5 - 25 3.5 2 Balance
OCT 0.3 - 14 3 - 2 35 3 - Balance
OCI - 5 14 1 3 - 12 2.5 - Balance

Several authors [22–28] have proposed that equivalent circuits are appropriate to study the main
corrosion processes occurring during a molten salt corrosion attack, providing different models, i.e.,
a localized corrosion model, a porous layer model, or a protective layer model.
After the electrochemical impedance spectroscopy (EIS) tests, a linear polarization resistance
(LPR) test was carried out. In this case, it was important to quantify the polarization resistance 𝑅
and the corrosion current density 𝑖 , given by Equation (2):
𝑩
𝒊𝒄𝒐𝒓𝒓 = (2)
𝑹𝒑
where B is an electrochemical constant calculated theoretically according to the Equation (3):
𝜷𝜶 ∙ 𝜷𝒄
𝑩= (3)
𝟐, 𝟑 ∙ 𝜷𝜶 + 𝜷𝒄
where 𝛽 and 𝛽 are the cathodic and anodic Tafel slope, respectively.
The corrosion rate (CR) could be estimated through the Butler–Volmer equation shown in
Equation (4):
 Coatings 2020, 10, 138 5 of 12

𝒊𝒄𝒐𝒓𝒓 ∙ 𝑲
𝑪𝑹 =
𝒇 ∙𝒏 (4)
𝝆𝒂𝒍𝒍𝒐𝒚 ∙ ∑ 𝒊 𝒊
𝑴𝑾𝒊
where 𝐾 is a correlation constant that defines the units of 𝐶𝑅 (3272 for 𝐶𝑅 in mm/year), 𝜌 is
the alloy density (g/cm ), 𝑓 is the mole fraction of element 𝑖 in the alloy, 𝑛 is the number of
3

electrons that are transferred in element 𝑖, and 𝑀𝑊 is the atomic weight of element 𝑖.

4. Results and discussion

Nyquist plots obtained for alloy OC4 are shown in Figure 2. The results were fitted to a
protective layer model after 1 and 3 h of immersion; the corrosion mechanism evolved to a localized
layer model after 5 h of immersion. An example of the fitting analysis carried out after 1 h of
immersion is shown in Figure 3.
Equivalent circuit element values for this material are shown in Table 3. These results were
confirmed by SEM analysis after the immersion test (Figure 4), indicating pitting corrosion (localized
corrosion model).

Figure 2. Nyquist diagram of alloy OC4 immersed in ternary chloride molten salt for 1, 3, and 5 h.

Table 3. Electrochemical parameters obtained from electrochemical impedance spectroscopy (EIS)

tests of OC4.

Element R3 (Ohm) Q1 (F/s) R5 (Ohm) Q2 (F/s) R7 (Ohm) Error (%) Equivalent circuit

1h 1.71 0.66 26.68 0.17 7.49 0.52

3h 1.45 0.26 1.11 0.19 63.94 0.41

Element R1 (Ohm) Q1 (F/s) R2 (Ohm) Q3 (F/s) R3 (Ohm)

5h 1.44 0.18 17.83 0.19 19.48 0.38

 Coatings 2020, 10, 138 6 of 12

Figure 3. Nyquist diagram of OC4 immersed in ternary chloride molten salt for 1 h and fitting analysis
to protective equivalent circuit analysis.

The scale formed during the corrosion process seemed to be protective and contained Fe-Al-Cr-
Ni-O. Nevertheless, pitting corrosion in the grain boundaries was observed at the end of the corrosion
test. This effect was detected by electrochemical impedance spectroscopy and suggested a localized
corrosion model.
Nyquist plots for alloy OCI are shown in Figure 5. The equivalent circuit obtained after 1 h (blue
line) of immersion indicated a protective corrosion model; however, after 3 and 5 h of immersion,
porous corrosion was detected. The results for the equivalent circuit elements are shown in Table 4.
A severe corrosion process with a corrosion layer thickness of 370 microns was observed, and these
results were confirmed by SEM (Figure 6).
In this case, the alloy did not generate an alumina coating on the steel surface, and the formation
of a porous corrosion layer was confirmed by electrochemical and scanning electron microscopy
techniques. The best results were obtained for alloy OCT, as it provided a protective corrosion model
during the immersion test. Nyquist plots and equivalent circuit elements for OCT are shown in Figure
7 and Table 5. The corrosion mechanisms observed at the end of the immersion test were confirmed
by SEM (Figure 8). In this case, a protective layer of 7.25 µm, containing Fe-Ni-Cr-O-Ti-Al, was
detected.

Table 4. Electrochemical parameters obtained from EIS tests of OCI alloy.

R3 Q1 R5 R7 Error
Element Q2 (F/s) Equivalent circuit
(Ohm) (F/s) (Ohm) (Ohm) (%)

1h 1.37 1.04 10.2 0.34 3.17 0.65

R1 Q1 R3 R5
Element W1
(Ohm) (F/s) (Ohm) (Ohm)
3h 1.38 0.07 12.92 0.02 1.84 0.58

5h 1.37 0.43 13.46 5.94 2.06 0.43

 Coatings 2020, 10, 138 7 of 12

Figure 4. Micrographs showing a top view (left) and a cross section (right) of OC4 immersed in ternary
chloride molten salt for 8 h at 720 °C; Energy dispersive X-ray (EDX) analysis on top.

Figure 5. Nyquist diagram of OCI immersed in ternary chloride molten salt for 1, 3, and 5 h.

Table 5. Electrochemical parameters obtained from EIS tests of OCT alloy.

R7
R3 Q1 R5 Q2 Error
Element (Ohm Equivalent circuit
(Ohm) (F/s) (Ohm) (F/s) (%)
)
1h 1.44 0.15 0.47e-9 0.26 44.38 0.45
3h 1.36 1.15 4.71 0.27 58.25 0.37

5h 1.36 0.46 19.18 0.44 36.92 0.31

Coatings 2020, 10, 138 8 of 12

Figure 6. Micrographs showing a top view (left) and a cross section (right) of OCI immersed in ternary
chloride molten salt for 8 h at 720 °C; EDX analysis is shown on top.

In order to confirm the corrosion layer composition obtained on the materials’ surface, an X-ray
diffraction (XRD) analysis was carried out for all the materials tested (Figure 9). The chemical
compounds obtained in the alloys immersed in chloride molten salts are shown in Table 6. Protective
layers were obtained for OCT, confirming the better corrosion resistance obtained for this material in
contact with chloride molten salt. This was confirmed by the corrosion mechanism detected using
EIS.
OCI showed porous corrosion, detected by EIS, and this was confirmed by the formation of non-
protective compounds such as Fe2O3, MgO, and MgOHCl on the alloy’s surface. These corrosion
products were confirmed by XRD (Table 6). The Tafel curves obtained for the AFA alloys are shown
in Figure 10. The screening test results for the materials are shown in Table 7.

Figure 7. Nyquist diagram of OCT immersed in ternary chloride molten salt for 1, 3, and 5 h.
Coatings 2020, 10, 138 9 of 12

Figure 8. Micrographs showing a top view (left) and a cross section (right) of OCT immersed in
ternary chloride molten salt for 8 h at 720 °C; EDX analysis is shown on top.

The linear polarization resistance technique was applied on the materials at 720 °C after 8 h of
immersion, obtaining a corrosion rate of 8.03, 21.55, and 7.61 mm/year for OC4, OCI, and OCT,
respectively.
The best corrosion resistance was obtained for OCT in accordance with the EIS results (protective
layer model) and the XRD/SEM results, which indicated that a protective layer consisting of MgAl2O4
and NiO formed on the surface of the steel. This internal layer formed in the OCT alloy acted as a
thermal diffusion barrier, avoiding the oxidation of constitutional elements in the tested alloy.

Figure 9. XRD analysis of OCT after 8 h of immersion in 20.4 wt.% KCl + 55.1 wt.% MgCl2 + 24.5 wt.%
NaCl at 720ºC.
Coatings 2020, 10, 138 10 of 12

Table 6. Corrosion products identified by XRD analysis on OC4, OCI, and OCT after immersion in
chloride molten salt at 720 °C for 8 h.

Corrosion Reference
Salt mixture Material
Products Pattern
FeCr2O4 00-024-0511
OC4
MgAl2O4 00-033-0853
Fe2O3 01-089-0597
MgCl2/NaCl/KCl (55.1 wt.% - 24.5 OCI MgOHCl 00-012-0120
wt.% - 20.4 wt.%) MgO 01-087-0651
MgAl2O4 00-033-0853
OCT NiO 03-065-6920
Fe3O4 01-086-1353

Table 7. Electrochemical parameters and corrosion rates obtained from the linear polarization
resistance (LPR) test for the tested materials.

Alloys Ecorr (mV) Icorr (mA) βc (mV) βa (mV) A (cm2) CR (mm/year)

OC4 −140.79 4258.75 322.1 651 4.46 8.03 ± 0.64
OCI −52.59 11429.4 398.9 524.9 4.53 21.55 ± 0.89
OCT −131.86 3837.05 407 902.2 4.41 7.61 ± 0.55

Figure 10. Tafel curves obtained from the LPR test for OCI, OC4, and OCT after 8 h of immersion in
chloride molten salt at 720 °C.

The Tafel curves, shown in Figure 10, confirmed the corrosion rates obtained in Table 7, since
the following anodic current order was determined: OCI > OC4 > OCT. The anodic current order was
directly related to the corrosion rate.

5. Conclusions
Alumina-forming alloys are a suitable option to generate protective coatings in a severe
corrosion environment. In this study, AFA alloys were examined after immersion in a ternary
chloride molten salt proposed as thermal energy storage (TES) material for CSP plants.
The linear polarization resistance technique was successfully applied to the tested materials, and
a down selection of AFA alloys was completed. The lower corrosion rate was obtained for the OCT
alloy using electrochemical impedance spectroscopy and was confirmed by SEM and XRD analyses.
It is also important to highlight that, by our XRD analysis, this alloy showed internal oxidation
Coatings 2020, 10, 138 11 of 12

characterized by the presence of a high amount of aluminum, which formed a protective barrier
composed of MgAl2O4. In a future research, previously oxidized OCT alloy will be subjected to longer
exposure times. The generation of alumina scales during the thermal cycles will be also analyzed,
since the coating formed on the CSP plant components needs to be stable during operation.
Author Contributions: L.F.C. and A.G.F. conceived and designed the experiments; L.F.C. and A.G.F. performed
the experiments and analyzed the data; A.G.F. wrote the paper. All authors contributed to the discussion and
obtained results. All authors have read and agreed to the published version of the manuscript.

Funding: This research received no external funding.

Acknowledgments: Angel G. Fernández would like to acknowledge the financial support from the European
Union’s Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grant No 712949
(TECNIOspring PLUS) and from the Agency for Business Competitiveness of the Government of Catalonia. This
work was partially funded by the Ministerio de Ciencia, Innovación y Universidades de España (RTI2018-
093849-B-C31 - MCIU/AEI/FEDER, UE) and the Agencia Estatal de Investigación (AEI) of the Ministerio de
Ciencia, Innovación y Universidades (RED2018-102431-T). The authors would like to thank the Catalan
Government for the quality accreditation given to their research group GREiA (2017 SGR 1537). GREiA is a
certified agent TECNIO in the category of technology developers from the Government of Catalonia. This work
is partially supported by ICREA under the ICREA Academia programme.

Conflicts of Interest: The authors declare no conflicts of interest.

References
1. Mehos, M.; Turchi, C.; Vidal, J.; Wagner, M.; Ma, Z.; Ho, C.; Kolb, W.; Andraka, C.; Kruizenga, A.
Concentrating Solar Power Gen3 Demonstration Roadmap; Technical Report; NREL/TP-5500-67464; 2017,
NREL, Golden , Colorado, USA.
2. Gomez-Vidal, J.C.; Fernandez, A.G.; Tirawat, R.; Turchi, C.; Huddleston, W. Corrosion resistance of
alumina-forming alloys against molten chlorides for energy production. I: Pre-oxidation treatment and
isothermal corrosion tests. Sol. Energy Mater. Sol. Cells 2017, 166, 222–233.
3. Gomez-Vidal, J.C.; Fernandez, A.G.; Tirawat, R.; Turchi, C.; Huddleston, W. Corrosion resistance of
alumina forming alloys against molten chlorides for energy production. II: Electrochemical impedance
spectroscopy under thermal cycling conditions. Sol. Energy Mater. Sol. Cells 2017, 166, 234–245.
4. Vignarooban, K.; Xu, X.; Wang, K.; Molina, E.; Li, P.; Gervasio, D.; Kannan, A.M. Vapor pressure and
corrosivity of ternary metal-chloride molten-salt based heat transfer fluids for use in concentrating solar
power systems. Appl. Energy 2015, 159, 206–213.
5. Fernandez, A.G.; Cabeza, L.F. Corrosion evaluation of eutectic chloride molten salt for new generation of
CSP plants. Part 1: Thermal treatment assessment. J. Energy Storage 2020, 27, 101125.
6. Brady, M.P. The development of alumina-forming austenitic stainless steels for high-temperature
structural use. JOM 2008, 60, 12–18.
7. Indacochea, J.E.; Smith, J.L.; Litko, K.R.; Karell, E.J. Corrosion performance of ferrous and refractory metals
in molten salts under reducing conditions. J. Mater. Res. 1999, 14, 1990–1995.
8. Garcia-Diaz, B.L.; Olson, L.; Martinez-Rodriguez, M.; Fuentes, R.; Colon-Mercado, H.; Gray, J. High
temperature electrochemical engineering and clean energy systems. J. South Carol. Acad. Sci. 2016, 14, 11–
14.
9. Ding, W. Judith Gomez-Vidal, Alexander Bonk, Thomas Bauer, Molten chloride salts for next generation
CSP plants: Electrolytical salt purification for reducing corrosive impurity level. Sol. Energy Mater. Sol. Cells
2019, 199, 8–15.
10. Ding, W.; Bonk, A.; Bauer, T. Corrosion behavior of metallic alloys in molten chloride salts for thermal
energy storage in concentrated solar power plants—A review. Front. Chem. Sci. Eng. 2018, 12, 564–576.
11. Eom, H.-C.; Park, H.; Yoon, H.-S. Preparation of Anhydrous Magnesium Chloride from Magnesium
Chloride Hexahydrate. Adv. Power Technol. 2010, 21, 125–130.
12. Huang, Q.; Lu, G.; Wang, J.; Yu, J. Thermal Decomposition Mechanisms of MgCl2·6H2O and MgCl2·H2O.
J. Anal. Appl. Pyrolysis 2011, 91, 159–164.
13. Skar, R.A. Chemical and Electrochemical Characterisation of Oxide/Hydroxide Impurities in the Electrolyte
for Magnesium Production. Ph.D. Thesis, Norwegian University of Science and Technology (NTNU),
Trondheim, Norway, 2001.
Coatings 2020, 10, 138 12 of 12

14. Ding, W.; Bonk, A.; Gussone, J.; Bauer, T. Electrochemical measurement of corrosive impurities in molten
chlorides for thermal energy storage. J. Energy Storage 2018, 15, 408–414.
15. Kashani-Nejad, S. Oxides in the Dehydration of Magnesium Chloride Hexahydrate; McGill University: Montréal,
QC, CA, 2005.
16. Ding, W.; Shi, H.; Xiu, Y.; Bonk, A.; Weisenburger, A.; Jianu, A.; Bauer, T. Hot corrosion behavior of
commercial alloys in thermal energy storage material of molten MgCl2/KCl/NaCl under inert atmosphere.
Sol. Energy Mater. Sol. Cells 2018, 184, 22–30.
17. Gomez-Vidal, J.C.; Noel, J.; Weber, J. Corrosion evaluation of alloys and MCrAlX coatings in molten
carbonates for thermal solar applications. Sol. Energy Mater. Sol. Cells 2016, 157, 517–525.
18. Audigié, P.; Bizien, N.; Baráibar, I.; Rodríguez, S.; Pastor, A.; Hernández, M.; Agüero, A. Aluminide slurry
coatings for protection of ferritic steel in molten nitrate corrosion for concentrated solar power technology.
AIP Conf. Proc. 2017, 1850, 0700021–0700028.
19. Kruizenga, A.M. Corrosion Mechanisms in Chloride and Carbonate Salts; Sandia Report; SAND2012-7594; 2012,
Sandia National Laboratories, Alburquerque, USA.
20. Hosoya, Y.; Terai, T.; Yoneoka, T.; Tanaka, S. Compatibility of structural materials with molten chloride
mixture at high temperature. J. Nucl. Mater. 1997, 248, 348–353.
21. Macdonald, D., Reflections on the history of electrochemical impedance spectroscopy. Electrochimica acta,
2006, 51, pp: 1376-1388.
22. Kisza, A. The capacitance of the diffuse layer of electric double layer of electrodes in molten salts.
Electrochim. Acta 2006, 51, 2315–2321.
23. Orazem, M.E.; Tribollet, B. An integrated approach to electrochemical impedance spectroscopy.
Electrochim. Acta 2008, 53, 7360–7366.
24. Zeng, C.L.; Wang, W.; Wu, W.T. Electrochemical impedance models for molten salt corrosion. Corros. Sci.
2001, 43, 787–801.
25. Fernández, A.G.; Rey, A.; Lasanta, I.; Mato, S.; Brady, M.; Perez, F.J. Corrosion of alumina-forming
austenitic steel in molten nitrate salts by gravimetric analysis and impedance spectroscopy. Mater. Corros.
2014, 65, 267–275.
26. Gao, G.; Stott, F.H.; Dawson, J.L.; Farrell, D.M. Electrochemical monitoring of high temperature molten salt
corrosion. Oxid. Met. 1990, 33, 79–94.
27. Rao, C.J.; Venkatesh, P.; Ningshen, S. Corrosion assessment of 9Cr-1Mo steel in molten LiCl-KCl eutectic
salt by electrochemical methods. J. Nucl. Mater. 2019, 514, 114–122.
28. Titz, J.; Wagner, G.H.; Lorenz, W.J. In situ EIS studies of localized corrosion processes in research and
industrial practice. Electrochim. Acta 1992, 37, 2309–2320.

© 2020 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).