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DOI 10.1007/s12666-016-0906-8
TECHNICAL PAPER
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reprocessing applications [610]. Ceramic coatings devel- emery papers up to 1200 grit. The polished specimens were
oped by plasma spray process on the structural materials grit blasted and 250 micron thick NiCrAlY interlayer
for pyrochemical reprocessing have been found to protect coating and 50 micron thick YSZ top coat were deposited
the substrate materials from molten salt corrosion. Besides by plasma spray process using a METCO 3 MB plasma
being corrosion resistant, the overlay coating on the sub- gun at M/s. Spraymet Surface Technologies Pvt. Ltd.,
strate is also expected to have good adhesion/bonding with Bengaluru. The plasma spray parameters used to deposit
the substrate, no interaction with the environment in which the coatings are given in Table 2. The coating was
it is used, minimum wettability and ability to withstand deposited on all faces of the rectangular specimens up to a
thermal cycles. height of 35 mm.
Periasamy et al. [11] evaluated the durability of ZrN and
HfN in molten LiClKClNaClUCl3 at temperatures 2.2 Molten Salt Corrosion Test
ranging from 525 to 900 C for durations in the range
4485 h under argon atmosphere. They observed that ZrN The electrorefining process in the pyrochemical repro-
and HfN experience weight loss under all experimental cessing of spent nuclear metallic fuels was carried out in
conditions due to the formation of volatile products and/or molten LiClKCl salt at 500 C. As the molten salt was
electrochemical dissolution. Formation of the volatile zir- highly hygroscopic, traces of moisture or oxygen present in
conium and hafnium chlorides may be attributed to the the molten salt would affect the performance of the elec-
reaction of the nitrides with chlorine gas or chloride ion, trorefining process. Therefore, actual pyrochemical repro-
which in turn is generated by the reaction of UCl3 species cessing was carried out in inert atmosphere glove boxes. To
present in the salt with oxygen. The corrosion behavior of simulate the real conditions of the electrorefining process,
yttria stabilized zirconia (YSZ) coating on various struc- the present study was carried out under inert argon atmo-
tural materials such as 2.25Cr1Mo steel, 9Cr1Mo steel, sphere. The LiCl (44.48 wt%)KCl (55.52 wt%) eutectic
Ni-based alloys 600, 625, and 690 has been studied by Ravi mixture was initially purified by passing chlorine gas at
Shankar et al. [4] and they reported that the YSZ-coated 500 C for about 30 min. Molten LiClKCl salt containing
specimens exhibit better corrosion resistance than the UCl3 was prepared by equilibrating uranium metal with
uncoated specimens; however, premature spallation of the cadmium chloride in LiClKCl eutectic salt at 500 C [13].
coating is observed, probably due to either imperfections in Uranium content in the LiClKClUCl3 salt was estimated
the coating or accidental ingress of oxygen and moisture by Davies and Gray method [14]. The LiClKCl molten
during the corrosion test. Recently, we have investigated salt containing 4 wt% UCl3, thus produced was loaded in a
the corrosion behavior of the structural materials, stainless recrystallised alumina crucible along with the 9Cr1Mo
steel 410 (SS 410), alloy 600 and 9Cr1Mo steel in LiCl steel specimens and thermocouple and the loaded crucible
KCl molten salt at 500 and 600 C by thermogravimetry in was sealed in a stainless steel cell inside an argon atmo-
inert (argon) and reactive (argon ? oxygen) atmospheres sphere glove box. The cell assembly containing 9Cr1Mo
and observed the attack by molten salt to be more in 9Cr steel specimens in the molten salt was heated in a furnace
1Mo steel than in SS 410, followed by alloy 600 under both to 600 C and corrosion testing was carried out for 100,
the atmospheres [12]. As the corrosion behavior of these 250, 500 and 1000 h under argon gas atmosphere. The
structural materials in high temperature molten LiClKCl uncoated and coated 9Cr1Mo steel specimens were tested
UCl3 salt has not been reliably reported in literature, the in the molten salt separately under identical experimental
present study has been undertaken to evaluate the corrosion conditions. Before and after the immersion test, the spec-
behavior of 9Cr1Mo steel and YSZ coated 9Cr1Mo steel imens were ultrasonically cleaned using water and acetone
in LiClKClUCl3 molten salt at 600 C under argon and allowed to air dry. The initial and final weights of the
atmosphere for their application in electrorefining process. specimens exposed to the molten LiClKClUCl3 salt were
recorded to assess the extent of corrosion.
2.1 Specimen Preparation During the course of corrosion test, the 9Cr1Mo steel
specimens were removed from the molten salt at various
The chemical composition of 9Cr1Mo steel specimen is durations such as 100, 250, 500 and 1000 h and were
given in Table 1. As-received and YSZ coated 9Cr1Mo examined visually. The surface morphology and elemental
steel specimens of dimensions 50 9 10 9 5 mm were analysis were carried out using scanning electron micro-
used for the corrosion studies in molten LiClKClUCl3 scope coupled with energy dispersive spectroscopy (SEM
salt. The 9Cr1Mo steel specimens were polished with SiC EDS, Mini SEM). The tested specimens were mounted in
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Table 2 Plasma spray parameters used for depositing NiCrAlY bond Fig. 1a, c, respectively. The 9Cr1Mo steel specimen
coat and YSZ top coat on 9Cr1Mo steel specimens before corrosion test appeared to be uniform with some
Process parameters (unit) NiCrAlY/YSZ coatings polishing lines and the corresponding EDS profile (Fig. 1b)
showed 9.03 wt% Cr, 1.00 wt% Mo and balance Fe. The
Plasma arc current (A) 450 SEM examination of the molten salt corrosion tested
Arc voltage (V) 60 uncoated 9Cr1Mo steel specimen revealed both porous
Primary gas Ar and corrosion product regions (Fig. 1c). The surface mor-
Secondary gas H2 phology with surface roughening indicated the dissolution
Powder feed rate (g/min) 4045 and etching of 9Cr1Mo steel. The attacked region showed
Spraying distance (mm) 100 porous structure, which might have formed due to the
Ar gas flow rate (l/min) 8090 removal or dissolution of alloying elements into the molten
Type of gun used 3 MB salt from the exposed surface. These dissolved elements
migrated to other regions of the substrate and formed the
corrosion product layer on the exposed surface of the
epoxy and used for cross-section examination and ele- substrate. Dissolution of metal at hot spot and metal
mental mapping by SEMEDS. X-ray diffraction (XRD) deposition at colder regions due to thermal gradient, as
patterns of the tested specimens were recorded using reported in literature [15, 16] upheld the observation in the
monochromatic Cu Ka radiation and the phases (corrosion present study.
products) were identified using the standard JCPDS files. The SEM images of the porous region of uncoated 9Cr
The XRD pattern of the 1000 h exposed sample was 1Mo steel specimens after molten salt exposure for 100,
obtained in glancing incidence X-ray diffraction (GIXRD) 250, 500 and 1000 h durations are shown in Fig. 2ad. It is
mode, while all the other samples were characterized by evident from these images that the extent of attack of the
normal XRD mode. 9Cr1Mo steel specimens increased with increase in the
duration of exposure to molten salt. Grain boundary attack
and grain pull out were visible in the SEM images. With
3 Results and Discussion increase in the exposure time, the attack became more
uniform and the attack was not only restricted to grain
3.1 Weight Loss Measurements boundary but also caused preferential surface dissolution.
The surface morphology of 1000 h exposed sample
The percentage weight loss of the uncoated 9Cr1Mo steel (Fig. 2d) showed a highly porous structure. The molten salt
specimens exposed to LiClKClUCl3 molten salt at 600 C attack and the leaching of alloy elements were higher for
for 100, 250 and 500 h durations were 0.5, 3.1 and 7.6, 1000 h exposed sample compared to other specimens. The
respectively. Weight loss of the specimens increased with increase in porosity could be due to higher penetration of
immersion time. The percentage weight loss for 100 h dura- molten salt that had resulted in the higher dissolution or
tion was higher compared to the percentage weight loss of leaching of alloying elements.
9Cr1Mo steel specimen (0.31) exposed to LiClKCl molten The SEM images of the corrosion product region of
salt for the same duration [4]. The percentage weight loss of 9Cr1Mo steel specimens exposed to molten salt for dif-
YSZ coated 9Cr1Mo steel specimens exposed to LiClKCl ferent durations are shown in Fig. 3ad. Significant quan-
UCl3 molten salt for different durations were insignificant. tity of corrosion products were observed as the duration of
exposure increased. Cracks were visible on the corrosion
3.2 Surface Characterization product region at higher magnification. No significant
difference was observed between the corrosion product
3.2.1 Uncoated 9Cr1Mo Steel Specimens regions of exposed samples for various durations. It is
observed from Figs. 2 and 3 that the surface morphology of
The SEM images of the uncoated 9Cr1Mo steel specimen 9Cr1Mo steel specimens exposed to molten salt for dif-
before and after the molten salt corrosion test are shown in ferent durations had similar features except that the
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Fig. 1 SEM image of a plain 9Cr1Mo steel substrate, b EDS elemental analysis of plain 9Cr1Mo steel substrate and c uncoated 9Cr1Mo
steel specimen after exposure to LiClKClUCl3 molten salt at 600 C for 100 h
corrosion attack was more penetrating and prominent all exposed surface had irregular and deep cavities, which
over the surface with increase in the duration of exposure. were visible at severely attacked regions. Some of the
The results of the EDS elemental analysis, given in regions were surrounded by corrosion product which could
Table 3 revealed that the porous and corrosion product be due to the preferential attack of grain boundaries. It
regions of the molten salt tested uncoated 9Cr1Mo steel could be inferred from the EDS analysis that selective
specimens had different chemical composition. The diffusion of Cr was the mechanism for the corrosion of
amount of Cr found in the corrosion product region was uncoated 9Cr1Mo steel in LiClKClUCl3 molten salt.
lower than that in the porous region, which could be
attributed to either the dissolution of Cr or the formation 3.2.2 Coated 9Cr1Mo Steel Specimens
of volatile Cr compounds. Presence of high oxygen con-
tent in the corrosion product region might be due to the The surface morphology of the as-received YSZ coated
formation of oxides of Fe and/or Cr. The oxygen content 9Cr1Mo steel specimens and those exposed to LiClKCl
in the argon cover gas was maintained at less than 2 ppm. UCl3 molten salt at 600 C for different durations of 100,
Formation of oxides of Fe and Cr were possible at low 250, 500, and 1000 h are shown in Fig. 5ae. After expo-
concentrations of oxygen [17]. Hence, the abundant cor- sure to molten salt the surface became more rough and
rosion products formed on the exposed surface of 9Cr some pores were formed. The surface morphology of the
1Mo steel specimens could be of iron oxide and chro- samples changed with increase in duration of molten salt
mium oxide. exposure, as shown in Fig. 5ae. The samples exposed for
Cross section examination of the tested uncoated 9Cr 100 and 250 h exhibited irregular surface than 500 and
1Mo steel specimens at different durations showed similar 1000 h exposed samples, probably because of the removal
features. The cross section image of the sample exposed to of loosely held coating particles from the surface after long
molten salt for 100 h duration is shown in Fig. 4. The exposure.
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Fig. 2 SEM images showing porous regions of uncoated 9Cr1Mo steel specimens after exposure to LiClKClUCl3 molten salt at 600 C for
a 100 h, b 250 h, c 500 h and d 1000 h
The standard Gibbs free energy change, DGr for the are shown in Fig. 6. In the EDS mapping, layers of coating
reactions of ZrO2 and Y2O3 with chlorine have been shown elements were visible in all the tested samples, indicating
in the reactions (1) and (2) [18]. Since the values of DGr for that even after corrosion test, the coating did not peel off
these reactions were positive at 600 C, no possible reaction from the specimen. However, in the case of 1000 h tested
was expected between the YSZ coatings and chlorine. sample, the YSZ coating thickness had reduced signifi-
cantly and became discontinuous (not found in some
ZrO2 2 Cl2 g ! ZrCl4 g O2 g; DGr kJ/mol locations). The bond coat was clearly distinguishable from
185 1 the EDS mapping of Ni and Al elements. As the bond coat
2 Y2 O3 6 Cl2 g ! 4 YCl3 g did not undergo any type of degradation and was intact on
3 O2 g; DGr kJ/mol the substrate, it was confirmed that the base metal had no
730 2 contact with molten salt, thereby preventing the corrosion
of 9Cr1Mo base metal.
The elemental analysis of the YSZ coated 9Cr1Mo steel
specimens tested in molten salt for 1000 h, by EDS (shown in 3.3 X-Ray Diffraction Analysis
Fig. 5f) confirmed the presence of elements from top coat
(YSZ), bond coat (NiCrAlY) and LiClKClUCl3 molten 3.3.1 Uncoated 9Cr1Mo Steel Samples
salt even after thorough cleaning of the samples for a couple
of times. Fe peaks detected on the tested YSZ coated Figure 7 shows the XRD patterns of uncoated 9Cr1Mo
specimens might be due to the deposition of iron oxide from steel specimens before immersion studies and after 100, 250,
the uncoated region of the specimen. Presence of uranium on 500 and 1000 h exposure in molten salt. The XRD results of
the tested YSZ coated specimens indicated that deposition of the 9Cr1Mo steel specimen before the molten salt exposure
salt had occurred on the surface of the coating. showed the peaks corresponding to FeCr (JCPDS no. 34-
The EDS elemental mapping of the cross sectional SEM 0396). The XRD results obtained for the exposed surfaces of
image of YSZ coated 9Cr1Mo steel specimen after uncoated 9Cr1Mo steel specimens were identical and the
exposure to molten LiClKClUCl3 salt for 100 h duration patterns revealed the presence of FeCr (JCPDS no. 34-
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Fig. 3 SEM images showing corrosion product regions of uncoated 9Cr1Mo steel specimens after exposure to LiClKClUCl3 molten salt at
600 C for a 100 h, b 250 h, c 500 h and d 1000 h
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Fig. 5 SEM images of a as-received and YSZ coated 9Cr1Mo steel specimens after exposure to LiClKClUCl3 molten salt at 600 C for
b 100 h, c 250 h, d 500 h and e 1000 h and f EDS elemental analysis of 1000 h exposed YSZ coated 9Cr1Mo steel specimens
2 UCl3 2 O2 g ! 2 UO2 3 Cl2 g; DGr kJ/mol and cubic phases. The X-ray diffraction patterns of YSZ
501600 C coated 9Cr1Mo steel specimens after exposure to LiCl
KClUCl3 molten salt for 100, 250, 500 and 1000 h are
3
shown in Fig. 8. All the XRD patterns showed the peaks
3.3.2 Coated 9Cr1Mo Steel Specimens corresponding to YSZ and UO2. The cubic and tetragonal
phases of ZrO2 were present and no phase transformation
The XRD pattern of as-sprayed YSZ coating on 9Cr1Mo of zirconia occurred after the exposure to molten LiCl
steel specimen, as shown in Fig. 8 consisted of tetragonal KClUCl3 salt.
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Fig. 6 EDS elemental mapping of YSZ coated 9Cr1Mo steel specimen after exposure to LiClKClUCl3 molten salt at 600 C for 100 h
duration
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References
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