Thermochimica Acta 653 (2017) 16–26

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Thermochimica Acta
journal homepage: www.elsevier.com/locate/tca

Study of phase equilibria in LiCl-KCl-PrCl3 pseudo-ternary system MARK

⁎,1
Sajal Ghosh, Rajesh Ganesan, R. Sridharan, T. Gnanasekaran
Materials Chemistry Division, Materials Chemistry and Metal Fuels Cycle Group, Indira Gandhi Centre for Atomic Research, Homi Bhabha National Institute, Kalpakkam
603 102, Tamilnadu, India

A R T I C L E I N F O A B S T R A C T

Keywords: The pseudo-ternary phase diagram of LiCl-KCl-PrCl3 has been investigated to understand the interaction of PrCl3
Metallic fuel reprocessing with LiCl-KCl molten salt medium by differential thermal analysis (DTA) technique and characterization of the
LiCl-KCl-PrCl3 coexisting phases in the solid state using X-ray diffraction (XRD). The results of these experiments showed that
Ternary phase diagram the LiCl-KCl-PrCl3 system consists of two quasi-ternary sections, namely (1) LiCl-KCl-K2PrCl5 section which has a
Differential thermal analysis
ternary eutectic temperature of 591 ± 4 K and approximate eutectic composition of 55.1 mol% LiCl-39.6 mol%
Isothermal section
KCl-5.3 mol% K2PrCl5 and (2) LiCl-K2PrCl5-PrCl3 section having a ternary eutectic temperature of 654 ± 7 K
Liquidus projection
and approximate eutectic composition of 46.8 mol% LiCl-32.2 mol% K2PrCl5-21.0 mol% PrCl3. A pseudo-ternary
peritectic reaction at 762 ± 1 K is observed at 22.3 mol% LiCl-39.6 mol% KCl-38.1 mol% K2PrCl5. Isothermal
sections at selected temperatures and the polythermal liquidus projection with isothermal contours are drawn
over the ternary phase field.

1. Introduction and also considering the data reported earlier by several authors. Basin
et al. [7] studied the phase diagram of LiCl-KCl system by thermal
Molten LiCl-KCl eutectic is used as liquid electrolyte medium in the analysis technique and combining the method of oscillation phase
pyrochemical reprocessing of spent metallic fuel [1]. In this process, analysis [8]. They reported the eutectic temperature as 625 K and
spent metallic fuel is dissolved in molten salt in the soluble chloride composition as 58.2 mol% LiCl and 41.8 mol% KCl. Liquidus tempera-
form and the fuel materials are selectively separated from fission tures, eutectic temperature, and composition reported by Basin et al.
products (FPs) by electrorefining [2,3]. Spent metallic fuel primarily [7] are in close agreement with those reported by previous investiga-
includes actinides, rare earth elements, noble metals, alkali and alkaline tors. In the present work, the phase diagram reported by Basin et al. [7]
earth elements, etc. The buildup of the anodically dissolved fission is considered for the construction of the pseudo-ternary phase diagram
products in the molten salt medium with time, could lead to the of the LiCl-KCl-PrCl3 system. The LiCl-KCl binary phase diagram
formation of high melting ternary or higher order compounds and reported by Basin et al. [7] is showed in Fig. 1.
result in the progressive increase of the liquidus temperature of the salt Kim and Okamoto [9] investigated the LiCl-PrCl3 binary phase
medium [4]. The increase in liquidus temperature can influence the diagram using differential thermal analysis (DTA) and X-ray diffraction
pyrochemical process parameters adversely. Praseodymium being one (XRD). They reported this phase diagram to be a simple eutectic type
of the major FP elements [5], it is necessary to understand the having the eutectic temperature as 737 ± 1 K and the composition as
interaction of PrCl3 in the LiCl-KCl medium and hence the study of 30.6 mol% PrCl3 – 69.4 mol% LiCl. Earlier, Qiao et al. [10,11]
phase equilibria in the LiCl-KCl-PrCl3 pseudo-ternary system is essen- investigated this system using DTA. They further assessed and opti-
tial. mized this binary system. They reported the system as simple eutectic
having a eutectic temperature of 739 K and eutectic composition of ca.
2. Literature survey 30 mol% PrCl3 – 70 mol% LiCl. Gong et al. [12] carried out thermo-
dynamic optimization of this binary system by PARROT program using
The LiCl-KCl binary phase diagram is a simple eutectic system. the reported experimental data [9–11]. The liquidus temperatures
Korin and Soifer [6] reported the binary eutectic temperature as reported by Qiao et al. [10,11] are about 30–40 K lower in the PrCl3
627.5 K and the composition as 58.7 mol% LiCl and 41.3 mol% KCl in rich region than the values reported by Kim and Okamoto [9]. Qiao
this system, based on their study using differential scanning calorimetry et al. [10,11] determined the liquidus temperatures during the cooling

⁎
Corresponding author.
E-mail addresses: [email protected], [email protected] (T. Gnanasekaran).
1
Raja Ramanna Fellow, Indira Gandhi Centre for Atomic Research, Homi Bhabha National Institute, Kalpakkam 603 102, Tamilnadu, India.

http://dx.doi.org/10.1016/j.tca.2017.03.024
Received 2 November 2016; Received in revised form 27 March 2017; Accepted 28 March 2017
Available online 30 March 2017
0040-6031/ © 2017 Elsevier B.V. All rights reserved.
S. Ghosh et al. Thermochimica Acta 653 (2017) 16–26

Fig. 3. KCl–PrCl3 pseudo binary phase diagram [13].

Fig. 1. LiCl–KCl pseudo binary phase diagram [7].

the samples containing < 17 mol% PrCl3, they identified LiCl, KCl, and
K2PrCl5 as coexisting phases below the solidus temperature. Based on
the DSC analysis of five samples containing < 17 mol% PrCl3, they
reported the ternary eutectic temperature at 625 K. Further, they
characterized LiCl and K2PrCl5 by XRD for the samples containing >
17 mol% PrCl3. They observed the solidus temperature as 681 K based
on the DSC analysis of three samples. They reported a step increase in
the solidus and liquidus temperatures for the sample containing 17 mol
% PrCl3, which falls on the isopleth connecting (LiCl-KCl) eutectic and
PrCl3 and attributed this to the existence of the LiCl and K2PrCl5
pseudo-binary line. This implies that the compound K2PrCl5 melts
congruently; and must undergo eutectic reaction with K3PrCl6, also. In
contrast, Seifert et al. [13] reported the peritectic decomposition of
K2PrCl5 at 890 K, which implies that LiCl and K2PrCl5 are expected to
form a non-binary join instead of a pseudo-binary eutectic. In view of
the above discrepancies reported in literature, the LiCl-KCl-PrCl3
ternary phase diagram needs a thorough investigation. Further, data
Fig. 2. LiCl–PrCl3 pseudo binary phase diagram [9]. on the primary and secondary crystallization temperatures as well as
the crystallizing phases and liquidus temperatures over the ternary
runs of DTA experiments. However, the rare earth containing salt phase field are not available. In this context, a detailed phase diagram
systems are known for supercooling. Hence, the lower values of the study on the LiCl-KCl-PrCl3 system was taken up in the author’s
liquidus temperatures may probably be attributed to the supercooling laboratory by DTA technique supported by XRD characterization of
effect in the DTA samples. Therefore, the phase diagram reported by the coexisting phases in the solid state.
Kim and Okamoto [9] is considered as more accurate and used in the
present ternary phase diagram construction. The LiCl-PrCl3 binary
3. Experimental
phase diagram reported by Kim and Okamoto [9] is shown in Fig. 2.
Seifert et al. [13] reported the KCl-PrCl3 binary phase diagram. It is
3.1. Materials
the only work available in the literature. They reported two ternary
compounds, viz. K2PrCl5 and K3PrCl6 in this system. The author
Details of the chemicals used in the study are given in Table 1.
reported K2PrCl5 to be stable from 573 K and undergoes peritectic
Anhydrous lithium chloride (99.995% pure, packed in sealed glass
decomposition to K3PrCl6 and liquid containing 34.5 mol% PrCl3 –
ampoules under argon, M/s Alfa Aesar, USA) and praseodymium
65.5 mol% KCl at 890 K. According to them, it undergoes a eutectic
chloride (99.99% pure, packed in sealed glass ampoules under argon,
reaction with PrCl3 at 772 K having a eutectic composition of 56 mol%
M/s Aldrich, Germany) were used in this work. Anhydrous potassium
PrCl3 – 44 mol% KCl. They also reported K3PrCl6 to be stable above
chloride (99.995% pure on the metals basis, M/s Alfa Aesar, Germany)
762 K and to be congruently melting. They reported a eutectic reaction
was further purified by heating it up to its melting point in a quartz
between K3PrCl6 and KCl at 886 K and the eutectic composition as
crucible, which in turn was placed inside a quartz vessel in a stream of
16.5 mol% PrCl3 – 83.5 mol% KCl. Gaune-Escard et al. [14] observed
dry HCl saturated argon gas. The details of salt purification are
the formation temperature of K3PrCl6 as 768 K from differential
described elsewhere [16]. The purified salt was placed inside a
scanning calorimetry studies and reported it to be congruently melting
secondary containment vessel and stored inside an argon atmosphere
at 944 K. The KCl-PrCl3 binary phase diagram reported by Seifert et al.
glove box used for handling molten sodium. The purity of these starting
[13] is shown in Fig. 3.
compounds, viz. LiCl, KCl, and PrCl3 were examined by carrying out
Literature data on the LiCl-KCl-PrCl3 system is limited. Nakamura
DTA studies. Sharp endotherms in the DTA traces of LiCl, KCl, and PrCl3
and Kurata [15] reported the partial phase diagram of the isopleth
were obtained and the melting points of LiCl, KCl and PrCl3 were found
connecting (LiCl-KCl) eutectic and PrCl3 (up to 25 mol% PrCl3) by
to be 878 K, 1045 K, and 1051 K, respectively. The observed melting
investigations involving thermal analysis, visual observation, electro-
points of LiCl, KCl and PrCl3 were in agreement with the data reported
motive force measurement and powder X-ray diffraction methods. For
in the literature [7,9–13,17–21].

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S. Ghosh et al. Thermochimica Acta 653 (2017) 16–26

Table 1
Source, purity, physical state of the chemicals used and purification method employed.

Compound Purity Physical state at the procurement stage Purification method

(Mass basis)

KCl 99.995% Anhydrous, packed in plastic bottle. Purified by passing HCl saturated argon through
(M/s. Alfa Aesar, Germany) molten KCl [16].
LiCl 99.99% Anhydrous, packed in sealed glass ampoules under argon atmosphere, Not further purified.
(M/s Alfa Aesar, USA) moisture content < 100 ppm (Used as procured)
PrCl3 99.99% Anhydrous, packed in sealed glass ampoules under argon atmosphere, Not further purified.
(M/s Aldrich, Germany) moisture content < 100 ppm. (Used as procured)

Table 2
Composition of samples in the ternary phase field, their equilibration temperatures and the phases identified by XRD at 0.1 ± 0.0001 M Pa pressure.

a a a b
Sample no. LiCl/mol% KCl/mol% PrCl3/mol% Equilibration Temperature/K Phases identified by XRD
( ± 1 K)

10 40 50 10 553 LiCl, KCl and K2PrCl5

19 30 50 20 553 LiCl, KCl and K2PrCl5
29 40 20 40 553 LiCl, K2PrCl5 and PrCl3
7 10 80 10 798 LiCl, KCl and K2PrCl5
19 30 50 20 798 LiCl, KCl and K2PrCl5

a
Expanded uncertainty (U) in composition is ± 0.1 mol% with confidence level of 0.95.
b
Period of equilibration at 553 K is 300 h in argon atmosphere; period of equilibration at 798 K is 24 h in argon atmosphere; uncertainty given is expanded uncertainty (U) with
confidence level of 0.95.

3.2. Equilibrations and XRD analysis (Part number 3 M, M/s. Scotch make, polyimide film). The holder was
taken out of the glove box and analyzed by XRD (Model number MPD
In order to identify the coexisting phases in the ternary system, 7501, M/s. Inel, France) using Cu Kα radiation. It is to be noted that the
appropriate amounts of LiCl, KCl and PrCl3 were mixed to prepare five XRD patterns of the samples sealed by this method did not deteriorate
samples (∼500 mg each) inside the argon atmosphere glove box. The by absorption of moisture, at least 4 h of exposure of the mounted
compositions chosen for this study are given in Table 2 and shown in sample holder to ambient air.
Fig. 4. They were loaded inside decarburized iron tubes (4 mm I.D.,
5 mm O.D. and 25 mm long) and hermetically sealed by pulsed arc TIG
3.3. Preparation of samples and DTA studies
welding. The iron tubes were in turn sealed in quartz tubes under high
vacuum. They were heated above the liquidus temperatures of the
Calculated amounts of LiCl, KCl, and PrCl3 were mixed to prepare
samples, which were determined from the DTA studies (see Sections
samples (∼500 mg each) of selected compositions for DTA studies. The
4.2.1 and 4.2.2) and maintained at that temperature for one hour for
compositions chosen for these samples are shown in Fig. 4, and the
homogenization. Three samples were cooled slowly to 553 K, which
details are given in Tables 3–5. Weighing and mixing of these samples
was below the lowest solidus temperature of all the samples, namely
were carried out in the inert atmosphere glove box. Sufficient amount
591 K (discussed in Sections 4.2.1 and 4.2.2) and equilibrated at that
of these samples (∼35 mg) were loaded inside decarburized iron tubes
temperature for 300 h followed by quenching in liquid nitrogen.
(2.5 mm I.D., 3.2 mm O.D. and 15 mm long), hermetically sealed by
Another two samples were equilibrated at 798 K for 24 h and quenched
pulsed arc TIG welding. They were heated to 1053 K under flowing
in liquid nitrogen. The samples were retrieved after cut opening the
hydrogen for homogenization and leak-checking. The samples were
iron tubes, followed by grinding them to powder using a mortar and
studied by DTA (Setsys Evolution 16/18 equipment, M/s. Setaram
pestle inside the argon atmosphere glove box. The powder samples
Instrumentation, France) at controlled heating and cooling rates. Argon
were loaded in the XRD sample holder and sealed by polymeric tape
– 4% hydrogen gas mixture at a flow rate of 20 ml min−1 was used as
carrier gas to prevent oxidation of the sealed iron tubes during the
experiments. DTA runs were recorded at a heating rate of 2, 3 and
5 K min−1 and in the temperature range between 523 and 1053 K,
while the cooling rate in all the runs was maintained at 3 K min−1.
Temperature calibration of the DTA unit was carried out using high
purity Sn, Zn, Al, and Au metal standards by measuring their melting
points. The expanded uncertainty (U) in the temperature measurement
was found to be within ± 1 K with a level of confidence of 0.95.

4. Results and discussion

4.1. XRD characterization of samples after high-temperature equilibrations

The samples (Table 2) after their equilibration at 553 K and 798 K

were characterized by XRD to deduce the coexisting phases. The onset
and completion temperatures of various thermal events deciphered
Fig. 4. Compositions of samples for equilibration studies [Δ] and DTA studies [●].
from the DTA studies are given in Tables 3–5. The lowest temperature
at which a thermal event occurred in these samples was observed at
591 ± 4 K. Pure LiCl, KCl, K2PrCl5 and PrCl3 do not show any thermal

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S. Ghosh et al. Thermochimica Acta 653 (2017) 16–26

Table 3
Solidus and liquidus temperatures of samples along the LiCl-K2PrCl5 isopleth (Heating rate 2 K, 3 K min−1) at 0.1 ± 0.0001 M Pa pressure in argon gas ambient.

a a a
Sample no. LiCl/mol% KCl/mol% PrCl3/mol% Solidus Temperature/K ( ± 2 K)b Liquidus Temperature (K) and dissolving phase
( ± 2 K)b

13 70 20 10 723 786, LiCl

18 40 40 20 723 792, K2PrCl5
22 10 60 30 700 867, K2PrCl5

a
Expanded uncertainty (U) in composition is ± 0.1 mol% with confidence level of 0.95.
b
Uncertainty given is expanded uncertainty (U) with confidence level of 0.95.

event up to 591 K. Hence, the observed thermal event at 591 ± 4 K is shows a change in the slope of the curve at the secondary crystallization
attributed to the lowest solidus temperature in this system, which is temperature.2
higher than the chosen equilibration temperature of 553 K. Further, Analysis of DTA traces of sample nos. 12 and 20 whose compositions
two samples were equilibrated at 798 K to investigate the formation of fall on the isopleth connecting LiCl and K3PrCl6 show the solidus
K3PrCl6. Analysis of XRD results of all the five samples showed the temperature as 591 ± 4 K and it is equal to the solidus temperatures of
absence of any quaternary compound. The results indicated the the adjoining samples whose composition do not fall on this isopleth
coexistence of LiCl, KCl, and K2PrCl5 at 553 K for the two samples (Table 4). If LiCl and K3PrCl6 form a pseudo-binary eutectic system, the
(nos. 10 and 19 in Table 2) whose compositions lie in the triangular solidus temperature of sample nos. 12 and 20 would have been more
region bound by LiCl, KCl, and K2PrCl5. XRD analysis of the single than the solidus temperature of the adjoining samples. Hence, it can be
sample (no. 29) whose composition lies in the triangular region bound concluded that sample nos. 12 and 20 are part of a larger ternary
by LiCl, K2PrCl5 and PrCl3 shows the coexistence of these three phases eutectic plane and LiCl and K3PrCl6 do not form a pseudo-binary line.
at 553 K. XRD pattern of this sample is shown in Fig. 5. The blank XRD Splitting of the peak at the first endotherm was not observed in the DTA
pattern of polymeric tape gave a hump below 30° (2θ), and this got traces of sample nos. 13, 18 and 22 (Fig. 6). These samples fall on the
superimposed upon XRD patterns of the samples. These results confirm LiCl-K2PrCl5 isopleth and their DTA characteristics are different from
that the isothermal section of the LiCl-KCl-PrCl3 system at 553 K those of the adjoining samples. The DTA traces of these three samples
consists of two quasi-ternary sections, namely (i) LiCl-KCl-K2PrCl5 are shown in Fig. 6. The composition, solidus and liquidus temperatures
and (ii) LiCl-K2PrCl5-PrCl3. Results of equilibration at 798 K showed of these three samples are given in Table 3. Analysis of the DTA traces
the coexistence of LiCl, KCl, and K2PrCl5. However, the formation of of these samples show the solidus temperature as 723 K, which is a step
K3PrCl6 at 763 ± 1 K could be delineated from the DTA traces of the increase from the solidus temperature of the adjoining samples
sample Nos. 7 and 21 (discussed in Sections 4.2.1 and 5.3). It is worth (Table 4 & 5). It can be noted that the solidus temperature of the
to mention that Seifert et al. [13] reported its formation temperature as samples with compositions rich in PrCl3 and beyond the LiCl-K2PrCl5
762 K. Therefore, it is proposed that K3PrCl6 would have decomposed isopleth also was observed at 654 ± 7 K (Table 5). Nakamura and
to K2PrCl5 and KCl upon quenching. Kurata [15] reported this elevated solidus temperature at 732 K and
attributed this to eutectic temperature between LiCl and K2PrCl5. But
4.2. DTA studies K2PrCl5 peritectically decomposes to K3PrCl6 and a liquid at 890 K as
per Seifert et al. [13]. Hence, it is very likely that LiCl and K2PrCl5 form
Solidus temperatures were deduced from the DTA traces by the a non-binary join instead of a pseudo-binary eutectic join. The LiCl-
onset extrapolation method. Appreciable supercooling effect was K2PrCl5 non-binary join section constructed using the present data as
observed in the cooling runs of DTA experiments. Hence, the liquidus well as the solidus and liquidus temperatures reported by Nakamura
temperatures were obtained from the analysis of the DTA traces of the and Kurata [15] is shown in Fig. 9. The thermal minima (m) and its
heating experiments only. The liquidus temperature was determined by composition were deduced as 723 ± 2 K and 56.6 mol% LiCl and
differentiating the DTA trace and noting the maximum in the differ- 43.4 mol% K2PrCl5, respectively, along the non-binary join. The
ential curve, near the tail end of the DTA trace. Typical DTA traces are cumulative error in composition of the thermal minima (m) is estimated
shown in Figs. 6–8. The first endotherms in Figs. 7 and 8 are attributed to be within 2 mol%.
to the respective ternary eutectic reaction involving the dissolution of
the three solids and appearance of liquid. One of the solids completely 4.2.1. LiCl-KCl-K2PrCl5 section
dissolves above the ternary eutectic temperature. It is to be noted that DTA results of the samples falling in the LiCl-KCl-K2PrCl5 section
the first endotherm corresponding to the ternary eutectic reaction (Fig. 10) are given in Table 4. This table provides the onset and
appears as split peaks instead of a sharp one. The split in the peak is completion temperatures of various endothermic thermal events deci-
attributed to the complexities involved in observing a ternary eutectic phered and the phases responsible for the thermal events observed in
reaction of isothermal melting of the three solids of different amounts the DTA traces. The first endothermic thermal event is assigned to the
together. Though the minimum possible sample size was taken, during solidus temperature. The mean of the solidus temperatures of all the
cooling of the samples after homogenization at 1053 K, solids would samples whose compositions lie in this section is found to be
have segregated near the walls of the crucible. During the DTA runs, the 591 ± 4 K. The uncertainty was deduced as the difference between
thermal event involves melting of the three solids simultaneously with mean and the farthest numerical value of the solidus temperature, with
different proportions depending on the composition studied. Para- a level of confidence of 0.95 (U). It was attributed to the ternary
meters such as heat capacity, thermal conductivity and the heat of
fusion of the three solids complicate the appearance of the shape of this
2
ternary eutectic peak. The sample homogeneity gets better as the liquid Appreciable super cooling effect is observed in cooling runs of DTA experiments.
Hence, various phase transition temperatures were deciphered from the heating runs of
phase appears above this temperature and no such complications were
DTA traces. The temperature at which the dissolution of the second solid phase is
seen in resolving the other thermal events. When the sample is heated completed would be same as the secondary crystallization temperature when cooling runs
above the ternary eutectic temperature, the dissolution of the second of DTA experiments are considered. To maintain conformity with the nomenclature used
and the third solid phases continue. Accordingly, the DTA pattern in the literature, we denoted this temperature as crystallization temperature.

19
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Table 4
Details of temperature and phases involved in various thermal events observed in the DTA traces of samples lying in the LiCl-KCl-K2PrCl5 section (Heating rate 2 K, 3 K min−1) at 0.1 ± 0.0001 M Pa pressure in argon gas ambient.

a a a
Sample no. LiCl KCl PrCl3 Ternary Phase dissolving K3PrCl6 formation Temperature (K) Secondary crystallization Temperature (K) and coexisting phases Phase dissolving above Liquidus
/mol% /mol% /mol% Eutectic above Ternary ( ± 1 K)b ( ± 2 K)b secondary crystallization Temperature (K)
Temperature (K) Eutectic Temperature Temperature and dissolving
( ± 4 K)b phase
( ± 2 K)b

Samples lying in the E1-KCl-K2PrCl5 area

4 45 50 5 591 LiCl – 682, L1 + KCl + K2PrCl5 KCl 690, K2PrCl5
10 40 50 10 591 LiCl – 633, L1 + KCl + K2PrCl5 KCl 763, K2PrCl5
20 20 60 20 589 LiCl 711, L1 + KCl + K2PrCl5 KCl 838, K2PrCl5
9 30 60 10 592 LiCl 737, L1 + KCl + K2PrCl5 KCl 758, K2PrCl5
7 10 80 10 592 LiCl 763 803, L6 + KCl + K3PrCl6 K3PrCl6 931, KCl
21 10 70 20 593 LiCl 762 882,

20
K3PrCl6
5 35 60 5 587 LiCl – 716, L1 + KCl + K2PrCl5 K2PrCl5 788, KCl
8 20 70 10 592 LiCl 761, L1 + KCl + K2PrCl5 K2PrCl5 853, KCl
6 20 75 5 591 LiCl – 737, L1 + KCl + K2PrCl5 K2PrCl5 915, KCl

Samples lying in the E1-LiCl-K2PrCl5 area

3 55.6 39.4 5 591 KCl – 626, L2 + LiCl + K2PrCl5 LiCl 675, K2PrCl5
11 50 40 10 591 KCl – 695, L2 + LiCl + K2PrCl5 LiCl 761, K2PrCl5
19 30 50 20 593 KCl – 706, L2 + LiCl + K2PrCl5 LiCl 811, K2PrCl5
2 65 30 5 590 KCl – 697, L2 + LiCl + K2PrCl5 K2PrCl5 733, LiCl
1 75 20 5 590 KCl – 709, L2 + LiCl + K2PrCl5 K2PrCl5 793, LiCl
12 60 30 10 591 KCl – – 736, LiCl

E1: Ternary eutectic in the LiCl-KCl-K2PrCl5 section.

a
Expanded uncertainty (U) in composition is ± 0.1 mol% with confidence level of 0.95.
b
Uncertainty given is expanded uncertainty (U) with confidence level of 0.95.
Thermochimica Acta 653 (2017) 16–26
S. Ghosh et al. Thermochimica Acta 653 (2017) 16–26

Table 5
Details of temperature and phases involved in various thermal events observed in the DTA traces of samples lying in the LiCl-K2PrCl5-PrCl3 section (Heating rate 2 K, 3 K min−1) at
0.1 ± 0.0001 M Pa pressure in argon gas ambient.

a a a
Sample no. LiCl KCl PrCl3 Ternary Phase Secondary crystallization Temperature (K) and coexisting phases Phase dissolving Liquidus
/mol% /mol% /mol% Eutectic dissolving ( ± 2 K)b above Temperature
Temperature (K) above secondary (K) and
( ± 7 K)b Ternary crystallization dissolving
Eutectic Temperature phase
Temperature ( ± 2 K)b

Samples lying in the E2-LiCl-K2PrCl5 area

26 50 20 30 654 PrCl3 677, L3 + LiCl + K2PrCl5 K2PrCl5 710, LiCl
16 60 20 20 658 PrCl3 706, L3 + LiCl + K2PrCl5 K2PrCl5 750, LiCl
14 80 10 10 660 PrCl3 709, L3 + LiCl + K2PrCl5 K2PrCl5 822, LiCl
25 40 30 30 654 PrCl3 691, L3 + LiCl + K2PrCl5 LiCl 745, K2PrCl5
24 30 40 30 653 PrCl3 698, L3 + LiCl + K2PrCl5 LiCl 793, K2PrCl5
23 20 50 30 647 PrCl3 710, L3 + LiCl + K2PrCl5 LiCl 841, K2PrCl5
17 50 30 20 659 PrCl3 – 759, K2PrCl5

Samples lying in the E2-K2PrCl5-PrCl3 area

30 30 30 40 656 LiCl 697, L4 + PrCl3 + K2PrCl5 PrCl3 722, K2PrCl5
29 40 20 40 652 LiCl 675, L4 + PrCl3 + K2PrCl5 K2PrCl5 739, PrCl3
31 20 30 50 651 LiCl 721, L4 + PrCl3 + K2PrCl5 K2PrCl5 807, PrCl3
32 30 20 50 650 LiCl 677, L4 + PrCl3 + K2PrCl5 K2PrCl5 857, PrCl3

Samples lying in the E2-LiCl-PrCl3 area

27 60 10 30 654 K2PrCl5 713, L5 + LiCl + PrCl3 PrCl3 724, LiCl
15 70 10 20 659 K2PrCl5 693, L5 + LiCl + PrCl3 PrCl3 775, LiCl
28 50 10 40 650 K2PrCl5 710, L5 + LiCl + PrCl3 LiCl 808, PrCl3
33 40 10 50 647 K2PrCl5 704, L5 + LiCl + PrCl3 LiCl 883, PrCl3

E2: Ternary eutectic in the LiCl-K2PrCl5-PrCl3 section.

a
Expanded uncertainty (U) in composition is ± 0.1 mol% with confidence level of 0.95.
b
Uncertainty given is expanded uncertainty (U) with confidence level of 0.95.

Fig. 5. XRD pattern of sample equilibrated at 553 K. Coexisting phases identified: LiCl,
K2PrCl5 and PrCl3 (Number in parenthesis corresponds to sample number).

eutectic temperature. This temperature was reported as 625 K by

Nakamura and Kurata [15]. It is expected that addition of a third
component to the LiCl-KCl binary system having the eutectic tempera-
ture of 625 K (e1) would decrease the solidus temperature below this
temperature. Hence, the observed solidus temperature of 591 ± 4 K
determined from the 15 different samples lying in this section is
considered to be reliable. Examination of the temperatures of thermal
events (Table 4) indicates that the liquidus and the secondary crystal-
lization temperature of sample number 3 are the lowest. Hence, the Fig. 6. DTA traces of the samples along the LiCl-K2PrCl5 isopleth (Heating rate: 2 K,
ternary eutectic composition of this section (E1) lies closer to the 3 K min−1). B → Solidus temperature, L → Liquidus temperature.

composition of sample number 3, i.e., 55.6 mol% LiCl-39.4 mol% KCl-

5 mol% PrCl3. The ternary eutectic point would lie between sample
number 3 and e1. The delineated composition of the ternary eutectic

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S. Ghosh et al. Thermochimica Acta 653 (2017) 16–26

Fig. 7. Representative DTA traces of samples lying in the LiCl-KCl-K2PrCl5 section

(Heating rate: 2 K, 3 K min−1). T → Ternary eutectic temperature, F → Compound Fig. 8. Representative DTA traces of samples lying in the LiCl-K2PrCl5-PrCl3 section
formation temperature, S → Secondary crystallization temperature, L → Liquidus tem- (Heating rate: 2 K, 3 K min−1). T → Ternary eutectic temperature, S → Secondary crystal-
perature. lization temperature, L → Liquidus temperature.

point, E1 is ca. 55.1 mol% LiCl-39.6 mol% KCl-5.3 mol% K2PrCl5. At the
ternary eutectic temperature, the chosen compositions of the samples in
the LiCl-KCl-K2PrCl5 section can further be grouped to be falling under
three areas, namely: (A) E1-LiCl-KCl, (B) E1-KCl-K2PrCl5 and (C) E1-
K2PrCl5-LiCl (Fig. 10). Since the ternary eutectic point, E1 lies close to
the e1, and the samples were prepared with a minimum of 5 mol%
PrCl3, none of the samples prepared in the present investigation lie in
the E1-LiCl-KCl area. The representative DTA traces of the seven
samples falling in the LiCl-KCl-K2PrCl5 section are shown in Fig. 7. In
these DTA traces, the first endotherm (which splits into two, discussed
in Section 4.2) is attributed to the ternary eutectic reaction involving
complete dissolution of LiCl or KCl for the samples, whose compositions
lie in the E1-KCl-K2PrCl5 region and E1-LiCl-K2PrCl5 region, respectively
in addition to the partial dissolution of the other two solids. The liquid
composition moves along the E1e4 (e4: eutectic between KCl and
K3PrCl6) and E1m monovariant lines, until the dissolution of the second
solid phase is completed at the secondary crystallization temperature.
The tail end of the endotherm observed in the DTA trace is ascribed to
complete dissolution of the remaining solid into liquid phase represent- Fig. 9. LiCl-K2PrCl5 non binary join section. m: 56.6 mol% LiCl and 43.4 mol% K2PrCl5.
ing the liquidus temperature. As an example, the thermal events
deciphered from the DTA traces of sample numbers 1 and 2 lying in
this section are described as follows. The first endotherms observed at line up to the secondary crystallization temperature, where K2PrCl5
590 K in the DTA traces of these two samples are attributed to the would dissolve completely. The solid composition moves along the m-
ternary eutectic melting involving the complete dissolution of KCl in LiCl line simultaneously. The secondary crystallization temperatures of
addition to the partial dissolution of LiCl and K2PrCl5 (Fig. 7). Hence, sample numbers 1 and 2 are observed at 709 K and 697 K, respectively.
they would have liquid (L) + LiCl + K2PrCl5 as coexisting phases Both the samples would have L + LiCl as coexisting phases above the
above 590 K. On further heating, LiCl and K2PrCl5 dissolve together, secondary crystallization temperature. On further heating, LiCl dis-
and the liquid composition would move along the E1m monovariant solves up to the liquidus temperature, which is observed as an

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S. Ghosh et al. Thermochimica Acta 653 (2017) 16–26

and secondary crystallization temperature closer to the ternary eutectic

temperature. Based on the analysis of the DTA traces of the samples in
this section, the ternary eutectic (E2) composition is delineated as ca.
46.8 mol% LiCl-32.2 mol% K2PrCl5-21.0 mol% PrCl3. The details of
invariant reactions, compositions and temperatures in the ternary phase
field are given in Table 6. Nakamura and Kurata [15] observed the
ternary eutectic temperature at 681 K for the three samples in this
phase field along the (LiCl-KCl)eutectic -PrCl3 isopleth. Based on the
compositions, the samples can be grouped to be falling under three
Fig. 10. Schematic diagram indicating the composition of the samples falling in the LiCl-
KCl-K2PrCl5 section. A: E1-LiCl-KCl area; B: E1-KCl-K2PrCl5 area; C: E1-LiCl-K2PrCl5 area,
areas, namely: (D) E2-LiCl-K2PrCl5, (F) E2-K2PrCl5-PrCl3 and (G) E2-
E1: 55.1 mol% LiCl, 39.6 mol% KCl, 5.3 mol% K2PrCl5. LiCl-PrCl3 at the ternary eutectic temperature as shown in Fig. 11. The
representative DTA traces of the six samples falling in this section are
endothermic tail end in the DTA traces of both the samples. The shown in Fig. 8. The first endotherm in the traces of heating runs of
liquidus temperatures of sample numbers 1 and 2 are deduced as 793 K DTA experiments can be ascribed to the ternary eutectic reaction
and 733 K, respectively. The DTA traces of sample nos. 7 and 21 show involving complete dissolution of either LiCl or K2PrCl5 or PrCl3 for
sharp endotherm at 762 ± 1 K (Table 4 and Fig. 7). It is attributed to the samples, whose composition lie in the E2-K2PrCl5-PrCl3, E2-LiCl-
the pseudo-ternary peritectic reaction ‘L + K3PrCl6 ↔ K2PrCl5 + KCl’. PrCl3 and E2-LiCl-K2PrCl5 regions, respectively in addition to the partial
The peritectic decomposition point of K2PrCl5 ‘p’ and the binary dissolution of the other two solids. Subsequent endoderm observed in
eutectic ‘e4’ between KCl and K3PrCl6 [13] are expected to invade in the DTA traces on further heating is attributed to the complete
the ternary phase field with the addition of LiCl. They would move dissolution of one of the solids namely, K2PrCl5 or PrCl3 in the E2-
along their respective monovariant lines and would meet at the pseudo- K2PrCl5-PrCl3 area, LiCl or PrCl3 in the E2-LiCl-PrCl3 area and LiCl or
ternary peritectic reaction point ‘P’. The deduced composition of the K2PrCl5 in the E2-LiCl-K2PrCl5 area. The liquid composition moves
point ‘P’ is approximately 22.3 mol% LiCl-39.6 mol% KCl- 38.1 mol% along the E2e3 (e3: K2PrCl5-PrCl3 binary eutectic), E2e2 (e2: LiCl-PrCl3
K2PrCl5. The results of the present investigation are in agreement with binary eutectic) and E2m monoivariant lines, respsctively until the
the KCl-PrCl3 binary phase diagram reported by Seifert et al. [13]. dissolution of the second solid phase is completed at the secondary
Hence, the data of the KCl-PrCl3 binary phase diagram reported by crystallization temperature. The tail end of the endotherm in the DTA
Seifert et al. [13] is used for the present LiCl-KCl-PrCl3 pseudo-ternary traces can be ascribed to the complete dissolution of the remaining solid
phase diagram investigation. to liquid, representing the liquidus temperature. For illustration, the
thermal events deciphered from the DTA traces of sample numbers 14
and 16 falling in this section are described as follows. The first
4.2.2. LiCl-K2PrCl5-PrCl3 section
endotherm observed at 654 ± 7 K in the DTA traces of these two
The DTA results of the samples falling in this section (Fig. 11) are samples are attributed to the end of the dissolution of PrCl3 in addition
given in Table 5. It provides the onset and completion temperatures of
to the partial dissolution of LiCl and K2PrCl5 (Fig. 8). Hence, they would
various endothermic thermal events delineated and the phases respon-
have L + LiCl + K2PrCl5 as coexisting phases above 654 K. On further
sible for the thermal events observed in the DTA traces of the samples.
heating, LiCl and K2PrCl5 dissolve together and the liquid composition
The average solidus temperature of the 15 samples lying in this section
moves along the E2m monovariant line (Fig. 11) up to the end of the
is found to be 654 ± 7 K which is considered as the ternary eutectic
dissolution of K2PrCl5 (secondary crystallization temperature) while
temperature. The reported uncertainty is the expanded uncertainty (U)
solid composition moves along the line, m-LiCl. The secondary crystal-
with a level of confidence of 0.95. Pure LiCl, K2PrCl5, and PrCl3 do not lization temperatures are observed at 709 K and 706 K in the DTA
show any thermal event up to 654 K. The DTA trace of a sample having
traces of sample numbers 14 and 16, respectively. Both the samples
composition around the ternary eutectic point should exhibit primary would have L + LiCl as coexisting phases above the secondary crystal-
lization temperature. On further heating, LiCl would dissolve up to the
liquidus temperature, which is observed as the endothermic tail end in
the DTA traces of these samples. The liquidus temperatures of sample
numbers 14 and 16 are deduced as 822 K and 750 K, respectively.

5. Isothermal sections construction at chosen temperatures

Various thermal events deciphered from the DTA traces of samples,

phases that coexist in the solid state and application of Gibbs phase rule
are the factors taken into consideration to draw the isothermal sections
at chosen temperatures. The phase boundaries were deduced based on
the thermal events observed in the DTA traces and interpolation of the
temperatures of various thermal events such as secondary crystal-
lization and liquidus temperatures of the adjacent samples.

5.1. Interpretation of DTA data of samples up to 673 K and construction of

isothermal section

5.1.1. LiCl-KCl-K2PrCl5 section

As mentioned in Section 4.2.2, the ternary eutectic temperature and
composition (E1) were observed at 591 ± 4 K and ca. 55.1 mol% LiCl-
39.6 mol% KCl-5.3 mol% K2PrCl5 in the LiCl-KCl-K2PrCl5 section. The
Fig. 11. Schematic diagram indicating the composition of the samples in the LiCl- secondary crystallization temperatures of sample numbers 3 and 10 are
K2PrCl5-PrCl3 section. D: E2-LiCl-K2PrCl5 area; F: E2-K2PrCl5-PrCl3 area; G: E2-LiCl-PrCl3 626 K and 633 K, respectively (Table 4). They would be in the two-
area. E2: 46.8 mol% LiCl, 32.2 mol% K2PrCl5, 21.0 mol% PrCl3. phase field consisting of L + K2PrCl5 at 673 K. Sample numbers 4–9, 20

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S. Ghosh et al. Thermochimica Acta 653 (2017) 16–26

Table 6
List of invariant reactions with approximate temperature and compositions in the LiCl-KCl-PrCl3 ternary system at 0.1 ± 0.0001 M Pa pressure in argon gas ambient.

Invariant reaction designation Reaction at the invariant point Temperature Reaction point compositionb

E1 (ternary eutectic) L ↔ LiCl + KCl + K2PrCl5 591 ± 4 Ka 55.1 mol% LiCl-39.6 mol% KCl-
5.3 mol% K2PrCl5
E2 (ternary eutectic) L ↔ LiCl + K2PrCl5 + PrCl3 654 ± 7 Ka 46.8 mol% LiCl-32.2 mol%K2PrCl5-21.0 mol% PrCl3
P (ternary pseudoperitectic) L + K3PrCl6 ↔ K2PrCl5 + KCl 762 ± 1 Ka 22.3 mol% LiCl-39.6 mol% KCl-38.1 mol% K2PrCl5

a
Uncertainty given is expanded uncertainty (U) with confidence level of 0.95.
b
Expanded uncertainty (U) in composition is ± 2.0 mol% with confidence level of 0.95.

Fig. 12. Tentative pseudo ternary LiCl-KCl-PrCl3 isothermal sections at (a) 673 K, (b) 723 K, (c) 773 K and (d) 873 K. L: liquid, a: KCl + K2PrCl5 + L1 (liquid in equilibrium with KCl and
K2PrCl5), b1: LiCl + K2PrCl5 + L2 (liquid in equilibrium with LiCl and K2PrCl5 in the LiCl-KCl-K2PrCl5 section), b2: LiCl + K2PrCl5 + L3 (liquid in equilibrium with LiCl and K2PrCl5 in the
LiCl-K2PrCl5-PrCl3 section), c: K2PrCl5 + PrCl3 + L4 (liquid in equilibrium with K2PrCl5 and PrCl3, d: LiCl + PrCl3 + L5 (liquid in equilibrium with LiCl and PrCl3), f: L + LiCl, g: L
+ KCl, h: L + K2PrCl5, i: L + PrCl3, j: KCl + K3PrCl6 + L6 (liquid in equilibrium with KCl and K3PrCl6), k: L + K3PrCl6, n: K3PrCl6 + K2PrCl5 + L7 (liquid in equilibrium with K3PrCl6
and K2PrCl5).

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S. Ghosh et al. Thermochimica Acta 653 (2017) 16–26

observations and shown in Fig. 12(b).

5.3. Interpretation of DTA data of samples from 723 K to 773 K and

construction of isothermal sections

Sample numbers 7 and 21 (Fig. 7) provide the evidence for the

formation of the high-temperature compound K3PrCl6 at 763 ± 1 K.
Seifert et al. [13] and Gaune-Escard et al. [14] reported its formation
temperature at 762 K and 768 K, respectively. The formation of K3PrCl6
leads to the appearance of three new phase fields above 763 K: (i) L
+ K3PrCl6 binary phase field, (ii) L + KCl + K3PrCl6 ternary phase
field and (iii) L + K3PrCl6 + K2PrCl5 ternary phase field. From the
results given in Tables 4 and 5, the following observations are made.
Sample number 7 would have L + K3PrCl6 + KCl as coexisting phases
at 773 K. Sample number 21 would be in the L + K3PrCl6 binary phase
field at 773 K. Sample numbers 20, 23 and 24 would be in the L
+ K2PrCl5 binary phase field at 773 K. Sample numbers 5, 6 and 8
would be in L + KCl binary phase field. Sample numbers 1, 14 and 15
would be in L + LiCl binary phase field at 773 K. Sample numbers 28,
31–33 would be in L + PrCl3 binary phase field at 773 K. Sample
Fig. 13. Polythermal liquidus projection with isothermal contours on LiCl-KCl-PrCl3 numbers 2, 9–12, 16, 17, 25, 27 and 29 would be in liquid phase at
system [——] indicates the extrapolated liquidus temperature.
773 K.
An isothermal section is constructed at 773 K taking into account
and 21 would have L + KCl + K2PrCl5 as coexisting phases; while the above observations and shown in Fig. 12(c).
sample numbers 1, 2, 11 and 19 would have L + LiCl + K2PrCl5 as
coexisting phases at 673 K (Table 4). 5.4. Interpretation of DTA data of samples from 773 K to 873 K and
construction of isothermal section
5.1.2. LiCl-K2PrCl5-PrCl3 section
The ternary eutectic temperature and composition (E2) was ob- Sample numbers 6 and 7 would be in the L + KCl binary phase field
served as 654 ± 7 K and ca. 46.8 mol% LiCl-32.2 mol% K2PrCl5- at 873 K. Sample numbers 21 and 33 would be in L + K3PrCl6 and L
21.0 mol% PrCl3 in the LiCl-K2PrCl5-PrCl3 section. None of the fifteen + PrCl3 binary phase fields, respectively at 873 K. Sample numbers 1,
samples present in this section show any thermal event from 654 K to 5, 8, 14, 15, 19, 20, 24, 28, 31 and 32 would be in liquid phase (Tables
673 K. Hence sample numbers 14, 16, 17, 23–26 would be in L + LiCl 4 and 5).
+ K2PrCl5 as coexisting phases at 673 K (Table 5). Sample numbers An isothermal section is constructed at 873 K considering the above
29–32 would be in L + K2PrCl5 + PrCl3 as coexisting phases at 673 K. observed coexisting phases and shown in Fig. 12(d).
Sample numbers 15, 27, 28 and 33 would have L + LiCl + PrCl3 as
coexisting phases at 673 K. 6. Liquidus projection
An isothermal section is constructed taking into account of the
observed coexisting phases at 673 K and shown in Fig. 12(a). Polythermal liquidus projection with isothermal contours of the
LiCl-KCl-PrCl3 system was drawn using (i) the liquidus temperatures
5.2. Interpretation of DTA data of samples from 673 K to 723 K and obtained from the traces of DTA experiments, (ii) the reported liquidus
construction of isothermal section temperatures of the binary systems that form the edges of the ternary
system and (iii) the guidelines given in Ref. [22]. The liquidus
5.2.1. LiCl-KCl-K2PrCl5 section projection, shown in Fig. 13 was drawn based on the isothermal
The secondary crystallization temperatures are less than 723 K for sections constructed from 673 K to 923 K at the interval of 50 K. Here,
sample nos. 1, 2, 3, 5, 11, 19 and 20 (Table 4). Hence, sample numbers contours from the corner of LiCl indicate the temperatures at which
1 and 2 would have L + LiCl as coexisting phases, 11, 19 and 20 would solid LiCl dissolve to give the complete liquid at those compositions.
have L + K2PrCl5 as coexisting phases; sample no. 5 would have L Similar contours are shown from the corners of KCl, PrCl3 as well as
+ KCl as coexisting phases at 723 K. Sample number 10 would from the position of K3PrCl6, which is formed at high temperature
continue to be in L + K2PrCl5 binary phase field. The liquidus (> 763 K). The expanded uncertainty (U) in composition in the
temperatures of sample numbers 3 and 4 are less than 723 K. They isothermal contour drawn is estimated to be within 2 mol% with 0.95
would be in liquid phase at 723 K. Sample numbers 5–9, 20 and 21 confidence level.
would continue to be in the L + KCl + K2PrCl5 ternary phase field.
7. Conclusion
5.2.2. LiCl-K2PrCl5-PrCl3 section
The secondary crystallization temperatures are less than 723 K for In the present investigations, coexisting phases in the solid state
all the samples lying in this section as shown in Table 5. Accordingly, were established by XRD characterization in the LiCl-KCl-PrCl3 pseudo-
sample numbers 14–16 and 27 would be in L + LiCl binary phase field. ternary phase diagram. There is no evidence of quarternary compound
Sample numbers 28, 29, 31–33 would be in L + PrCl3 binary phase formation in the LiCl-KCl-PrCl3 ternary system. LiCl and K2PrCl5 form a
field, and sample numbers 23–25 would be in L + K2PrCl5 binary phase non-binary join. The ternary phase diagram consists of two quasi-
field. The liquidus temperature of sample numbers 26 and 30 are less ternary systems namely, LiCl-KCl-K2PrCl5 and LiCl-K2PrCl5-PrCl3. The
than 723 K, and they would be in liquid phase at 723 K. ternary eutectic temperature in the LiCl-KCl-K2PrCl5 quasi-ternary
As the LiCl-K2PrCl5 non-binary join thermal minima is 723 ± 2 K, section is 591 ± 4 K and the eutectic composition is ca. 55.1 mol%
liquids from both the LiCl-KCl-K2PrCl5 and LiCl-K2PrCl5-PrCl3 sections LiCl-39.6 mol% KCl-5.3 mol% K2PrCl5. The pseudo-ternary peritectic
would meet at this thermal minima point (m). reaction ‘L + K3PrCl6 ↔ K2PrCl5 + KCl’ is deduced at 22.3 mol% LiCl-
An isothermal section is constructed at 723 K based on the above 39.6 mol% KCl- 38.1 mol% K2PrCl5 at 762 ± 1 K. The eutectic tem-

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S. Ghosh et al. Thermochimica Acta 653 (2017) 16–26

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