Corrosion Science 48 (2006) 679695 www.elsevier.

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Thermodynamic and kinetic consideration on the corrosion of Fe, Ni and Cr beneath a molten KClZnCl2 mixture
Andreas Ruh, Michael Spiegel
*
Max-Planck-Institut fur Eisenforschung GmbH, Max-Planck-Str. 1, D-40237 Dsseldorf, Germany u Received 18 August 2004; accepted 3 February 2005 Available online 12 May 2005

Abstract Thermogravimetric (TG) experiments have been carried out to study the kinetics of hot corrosion of Fe, Cr and Ni, covered by a molten KClZnCl2 mixture of a composition close to the eutectic (50 mol% KCl50 mol% ZnCl2). Furthermore binary and ternary phase diagrams were calculated in order to describe the corrosion process. The tests were conducted at a temperature of 320 C in an atmosphere consisting of argon and oxygen. For iron dierent stages are observed in a TG curve. They can be attributed to the dierent reaction steps of iron chloride formation (incubation phase), oxide precipitation (linear stage) and scale formation (parabolic or logarithmic stage). Based on these observations a model, described by Spiegel [A. Spiegel, Molten Salt Forum 7 (2003) 253], is conrmed. For Cr and Ni these stages are not observed. At 8 vol% O2 only slight oxidation of Cr and Ni was observed accompanied by evaporation of the salt deposit. At 16 vol% O2 the rate of oxidation increases and the experiments yield a curve that is either parabolic or logarithmic for both Ni and Cr. As a result it is shown that the solubility of iron chloride in the KClZnCl2 melt is higher than the solubility of nickel chloride and chromium (III) chloride in the KClZnCl2 melt. This enables a higher diffusibility of iron chloride to the upper region of the melt where a higher oxygen partial pressure (p(O2)) is present leading to a higher oxidation rate of iron. 2005 Elsevier Ltd. All rights reserved.

Corresponding author. Tel.: +49 211 6792 915; fax: +49 211 6792 218. E-mail addresses: ruh@mpie.de (A. Ruh), spiegel@mpie.de (M. Spiegel).

0010-938X/$ - see front matter 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.corsci.2005.02.015

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Keywords: C. Hot corrosion; C. Thermodynamic diagrams; A. Molten salts; A. Iron; A. Nickel

1. Introduction Operation of waste incinerators is associated with the production of corrosive gases and aerosols, which condense on the surface of boiler tube walls as salt deposits [2]. Heavy metal compounds are present that form eutectic salt mixtures with low melting points. The corrosive gases and the molten salt deposit both result in accelerated corrosion. In addition, economical aspects and political requirements that demand an increase of the quota of regenerative energy to 12% of the total energy production by the year 2010, require reliability and safety in operating such plants. Salt induced corrosion has initially been investigated for sulfate deposits (e.g. [3]). A review of sulfate melt-induced corrosion is given by Rapp [4]. The presence of molten sulfates on the steel surface leads to increased corrosion caused by the dissolution of the passivating oxide layer in the sulfate melt. As increased corrosion also takes place for steels covered with chloride deposits, corrosion studies for chloride systems have also been undertaken. Reese and Grabke [5,6] investigated the corrosive inuence of solid chlorides (KCl, NaCl, MgCl2 and CaCl2) on the high temperature corrosion of alloys. In this experiments, carried out at 500 and 700 C in HeO2 and HeO2SO2 atmospheres, ferrate or chromate formation as well as release of chlorine, caused by a solid state reaction of the salt with the oxide scale of the preoxidised sample, could be observed. Chlorine diuses through cracks and pores of the oxide scale to the metal/scale interface and reacts with the metal to form solid FeCl2. The vapour pressure of FeCl2 reaches 104 bar at 500 C and the volatile iron chloride diuses outward through the oxide scale. At the oxide/gas interface formation of iron oxide takes place, releasing further Cl2. The growth of iron oxide inside cracks and pores of the oxide scale leads to destruction of the scale and corrosive gases react with the unprotected metal. A generally non-passivating scale is formed on the metal substrate. For this reason the mechanism initially described by Lee and McNallan [7] was originally called active oxidation. As no chlorine is consumed in this process, it plays a catalytic role. Reese and Grabke [5] concluded from thermogravimetric experiments that evaporation of FeCl2 from the metal/scale interface is the rate determining step in NaCl induced corrosion. Spiegel [1] observed increased mass gain in TG tests investigating the oxidation of 2.25Cr1Mo at 500 C and 600 C using pure PbCl2 and ZnCl2 deposits in comparison to pure oxidation without deposit. At these temperatures both chlorides exist in liquid form. Enhanced mass gain is also discovered at lower temperatures (350400 C) when a eutectic chloride mixture (e.g. KClZnCl2) is used. In recent years corrosion studies have also been carried out on pure Cr covered with solid and liquid chlorides. The KCl induced corrosion behaviour of pure Cr

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was studied by Li et al. [8]. At 650 C strongly enhanced oxidation of pure Cr covered by a KCl deposit was observed in an atmosphere containing KCl vapour in comparison to a purely oxidising environment. Additionally the corrosion behaviour of pure Cr interacting with a solid NaCl deposit was investigated at 500700 C by Shu et al. [9]. Kinetic experiments have shown that a solid NaCl deposit on the surface signicantly accelerates the corrosion of pure Cr in air or oxygen mixed with water vapour. However, corrosion of pure Cr in air or in O2 mixed with water vapour at 500700 C was not signicant because of the formation of protective Cr2O3 on the surface. It was pointed out that the reaction of NaCl with the oxide and metal substrate is a reason for the accelerated corrosion, as the protectiveness of Cr2O3 scale was destroyed. Corrosion behaviour of pure Fe, Ni, Cr and Fe-based alloys covered by ZnCl2KCl has been tested by Li et al. [10]. The experiments were carried out at 450 C in pure oxygen. This atmosphere is very dierent from the atmosphere in waste incinerators. Since severe corrosion may occur even at lower temperatures, further experiments at lower temperature are necessary with an oxygen content that is closer to the atmosphere inside waste incinerators. The working model for corrosion beneath molten chloride is given in Fig. 1 [11]. In that model corrosion starts with the dissolution of the metal at the substrate/salt melt interface and the formation of iron chloride. Disregarding any chlorine in the gas phase, the chlorine source must be the molten chlorides. In this case chlorine can be released by the oxidation of the chloride. The produced iron chloride can diffuse outward to the salt melt/gas atmosphere interface. At the outer region of the salt a higher oxygen partial pressure is present, which allows the oxidation of FeCl2 to Fe2O3 and Cl2 due to its favoured thermodynamic stability. The recreated chlorine diuses back to the metal/salt melt interface and allows a subsequent formation of iron chloride. Equal to the corrosion process induced by solid chlorides [5,6] chlorine is not consumed and thus this process is catalysed by chlorine.

gas flow

Ar O2
2

p(O2)

p(Cl2)

3 2FeCl2 + O2 = Fe2O3 + 2Cl2

melt metal

Fe + Cl2

FeCl2 (dissolution) Fe

Fig. 1. Schematic model of chloride melt induced high temperature corrosion process [11], showing the transport of gas species and chemical reactions forming iron oxide and iron chloride (as described in the text).

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2. Experimental The corrosion kinetics of chloride melt-induced corrosion has been studied by thermogravimetric experiments. The samples were rst cut into specimens of about 10 10 $2.53 mm, then roughly polished using SiC grinding paper (Grit 1000) and nally polished to a mirror image using diamond paste. Subsequently the samples were cleaned in an ultrasonic bath lled with acetone and dried by hot air. Prior to carrying out the experiment the polished samples were covered with a 50 mol% ZnCl250 mol% KCl salt deposit, a composition close to the lowest eutectic melting point of about 250 C [2]. The amount of the salt deposit has been varied [030 mg/cm2] throughout the experiments. The TG tests have been conducted at 320 C in an atmosphere of Ar mixed with O2 (0, 4, 8 and 16 vol%). The tests in pure argon have been done to study the evaporation of the chloride melt deposit. The ow rate of the reaction gas was 2.5 ml/s. The heat up of the specimen was done in Ar and the reaction gases were added as soon as the reaction temperature was reached and the balance reached a stable state. After the experiments the corrosion products have been examined using atomic absorption spectroscopy (AAS), X-ray diraction (XRD) and scanning electron microscopy (SEM).

3. Results 3.1. Experiments with iron Hot corrosion of pure Fe covered with ZnCl2KCl melt shows three kinetic steps, described by Ruh and Spiegel [11]. The stages are clearly seen in the TG curve (Fig. 2). At the beginning corrosion starts slowly (incubation phase). After that the corrosion process accelerates. This is accompanied by a high mass gain. During this stage the TG curve follows a linear rate law. Finally, the reaction slows down and the TG curve follows a rate law that is either parabolic or logarithmic. In comparison to tests with uncovered samples (Fig. 3) the corrosion is aggravated and enhanced mass gain is observed. The corrosion products were examined by using SEM with EDX (Fig. 4) and XRD. The formation of iron chloride is the major reaction during the incubation phase. Only little oxide formation occurs at this stage but increases rapidly during the linear stage. During the outset of corrosion the formation of Zn-bearing magnetite was detected by XRD. After a longer corrosion time hematite is the predominant corrosion product. In both cases the oxide is present as precipitate embedded inside the molten KClZnCl2FeCl2 mixture, as seen in metallographic cross-sections and identied by EDX and XRD. Additionally the amount of the water soluble fraction, which corresponds to the amount of iron chloride, has been determined by AAS after dierent reaction times (296 h). The amount increases during the rst 48 h of corrosion but decreases when the reaction time is longer than 48 h (Fig. 5). This is caused by consumption of iron

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15

C C
mass gain [mg/cm2]
2 mass gain [mg/cm2]]

15

10

C C
10

B B
5

B B
5

A A
0 0 02 2 4
time [h]

10

A A
0 20 40 60 80 100

time [h]
Fig. 2. TG curve for high temperature corrosion (T = 320 C) of pure Fe covered with a 50 mol% KCl 50 mol% ZnCl2 deposit in an Ar + 4 vol% O2 atmosphere. A, B and C are dierent kinetic stages. The small plot gives a snap-shot of the rst 10 h of this experiment.

0.2

A 16 vol.% O2
mass gain [mg/cm2] 0.15

B 8 vol.% O2

0.1

A
0.05

B
0 0 20 40 60 time [h]
Fig. 3. TG curves for high temperature corrosion (T = 320 C) of pure Fe without a salt deposit in an Ar O2 atmosphere (8 and 16 vol%). Mass gains are negligibly small in comparison to tests with the ZnCl2 KCl deposit (see Fig. 2).

80

100

120

chloride in the oxidation process. In general the slight mass changes of iron chloride conrm to the slight mass gains observed in TG experiments after 24 h. It is important to note that the formation of iron chloride itself would not cause any mass gain

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Fig. 4. Left: SEM overview micrograph of pure Fe after 4.45 h of corrosion beneath molten ZnCl2KCl salt mixture (15 mg/cm2) in Ar8 vol% O2 at 320 C. The upper scale consists of porous and non-protective iron oxide (hematite) having a needle-like structure and minor amounts of chlorine incorporated into it. Right: Metallographic cross-section of the same sample. Scale consists of two layers with ne precipitated oxide embedded inside the molten chloride.

2.0

1.5 Cr/Ni/Fe [mg/cm2]

1.0

Cr Ni Fe

0.5

0.0 0 20 40 time [h] 60 80 100

Fig. 5. Amounts of Fe, Cr and Ni in the water soluble parts of the scale after 296 h of corrosion. Their amounts correspond to the amount of their chlorides. The dissolution of chromium increases signicantly after 48 h of corrosion while the amount of iron chloride decreases slightly during these long corrosion times. The amount of nickel chloride shows a marginal increase after about 50 h.

at all, because the chlorine is delivered by the melt itself and only slight amounts of oxygen are picked up by the KClZnCl2 melt. If the reaction proceeds and as soon as the iron chloride diuses to the melt/gas interface, oxide is formed and mass increases rapidly, as seen in the linear stage.

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The incidence of the kinetic stages (average values) is strongly dependent on the gas atmosphere and the amount of salt deposit. Fig. 6 shows that the duration of the incubation phase decreases with increasing oxygen partial pressure (p(O2)) and increases with increasing amount of salt deposit. The linear rate constant of the subsequent stage is also dependent on both the amount (thickness) of the salt deposit and p(O2) (Fig. 7). The values given here are also average values. While the inuence of the amount of oxygen on the total mass gain after a certain time of corrosion is quite small, the thickness of the molten chloride deposit considerably inuences the total mass gain. Using 30 mg/cm2 of the ZnCl2KCl salt mixture the total mass gain approximately doubles in comparison to experiments with 15 mg/cm2 of the ZnCl2KCl deposit.

3 Incubation time [h]

Salt deposit:
15 mg/cm2

30 mg/cm2

0 0 4 8 12 16 20 O2 [vol.%]
Fig. 6. Duration of the incubation time in dependence on the amount of oxygen and the amount of KCl ZnCl2 deposit (average values). Incubation time decreases with increasing amount of O2 and increases with increasing amount of KClZnCl2 deposit.

80 60 40 20 0 0 5 10 time [h]
Fig. 7. Dependence of the linear rate constant on the amount of oxygen and salt deposit (average values). Klin increases with increasing amount of oxygen and decreases with increasing amount of salt deposit.

klin [mg/cm2*h]

Salt deposit:
15 mg/cm2

30 mg/cm2

15

20

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3.2. Experiments with nickel The corrosion of Ni covered by molten chloride deposit is less severe than the corrosion of Fe (Fig. 8). At 320 C the corrosion test on Ni covered by a 15 mg/cm2 ZnCl2KCl deposit in Ar8 vol% O2 even yields a mass loss. Comparison with the experiments of Fe and Pt covered with a KClZnCl2 deposit in an inert Ar atmosphere demonstrates that the mass loss in this experiment is due to the evaporation of the molten salt deposit. Slight oxidation takes place nevertheless since the mass loss in the case of Ni in Ar8 vol% O2 is lower than in the case of Fe and Pt heated in Ar. An increase of the oxygen content to 16 vol% leads to a signicant higher oxidation rate as well as an increase in thickness of the chloride deposit to 30 mg/cm2. The metallographic cross-section of corroded Ni samples shows scales, which are still predominated by molten chloride (Fig. 9). Formation of nickel chloride is evident. Nickel oxide occurs as ne precipitations in small quantities. For a higher amount of the salt deposit a higher amount of nickel oxide is observed together with the formation of nickel chloride (Figs. 10 and 11). As in the experiments with Fe in the case of Ni the water soluble fraction has also been analysed chemically by AAS (Fig. 5). Its amount, which corresponds to the amount of Ni chloride, increases very slightly with increasing reaction time. 3.3. Experiments with chromium Corrosion tests with Cr show little mass gain. It increases slightly when the oxygen amount is increased from 8 vol% to 16 vol% (Fig. 12). Application of 30 mg/cm2

3 2 mass gain [mg/cm2] 1 0 -1 -2

1 2 3
real m

1 2 3 4

Ni 16 vol.% O2 15 mg/cm2 ZnCl2/KCl Ni 8 vol.% O2 30 mg/cm2 ZnCl2/KCl Ni 8 vol.% O2 15 mg/cm2 ZnCl2/KCl Fe 0 vol.% O2 30 mg/cm2 ZnCl2/KCl Pt 0 vol.% O2 30 mg/cm2 ZnCl2/KCl

4 5 5
120

-3 0 20 40 60 time [h] 80 100

Fig. 8. TG curves for high temperature corrosion (T = 320 C) of pure Ni covered with dierent amounts of a 50 mol% KCl50 mol% ZnCl2 deposit in an ArO2 atmosphere (8 and 16 vol%). Tests on Pt and Fe covered with ZnCl2KCl in an inert Ar atmosphere are shown to illustrate the evaporation rate of the chloride deposit. Another test result on Fe with 15 mg/cm2 ZnCl2KCl in inert gas atmosphere is identical to that with 30 mg/cm2 ZnCl2KCl.

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Fig. 9. Metallographic cross-section of pure Ni after reaction (126 h) beneath 50 mol% ZnCl250 mol% KCl (15 mg/cm2) in Ar16 vol% O2 showing a porous layer of molten chloride together with small amounts of ne precipitated nickel oxide. EDX analysis indicates the presence of nickel chloride.

Fig. 10. Left: SEM micrograph of pure Ni after reaction (123 h) beneath molten ZnCl2KCl salt mixture (30 mg/cm2) in Ar8 vol% O2 at 320 C showing a KZn chloride melt (smooth surface) and KNi chloride regions with minor amounts of Zn (1). Right: Salt melt poor part of the surface of the same Ni sample showing nickel oxide as predominant phase.

of the ZnCl2KCl mixture slightly enhances the mass gain in comparison to the experiment where 15 mg/cm2 ZnCl2KCl was applied. It must be mentioned that the real mass gains may be higher because of evaporation of the chloride deposit similar to the Ni experiments. After the experiment the samples have been investigated using SEM. Part of a partially spalled scale shows some rod-shaped chromium oxide grown on the chloride melt (Fig. 13, left). Metallographic cross-sections exhibit scales similar to those exhibited by corroded Ni. They show predominantly the chloride melt (Fig. 13, right). EDX analysis indicates the presence of chromium oxide and chromium chloride.

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Fig. 11. Metallographic cross-section of pure Ni after 123 h of reaction beneath molten ZnCl2KCl deposit (30 mg/cm2) in Ar8 vol% O2 showing a NiO-rich layer (1), Ni-poor chloride melt layers (2+4) and signicant precipitation of nickel oxide (3) within the molten chloride layer.

1
3

Cr 8 vol.% O2 30 mg/cm2 ZnCl2/KCl Cr 16 vol.% O2 15 mg/cm2 ZnCl2/KCl Cr 8 vol.% O2 15 mg/cm2 ZnCl2/KCl Fe 0 vol.% O2 30 mg/cm2 ZnCl2 /KCl Pt 0 vol.% O2 30 mg/cm2 ZnCl2/KCl

mass gain [mg/cm2]

2 1 0 -1 -2 -3 0 50 100

1 2

2 3 3

4 5

real m

4 5
150

time [h]
Fig. 12. TG curves for high temperature corrosion (T = 320 C) of pure Cr covered with dierent amounts of a 50 mol% KCl50 mol% ZnCl2 deposit in an ArO2 atmosphere (8 and 16 vol%). Tests on Pt and Fe covered with ZnCl2KCl in an inert Ar atmosphere are shown to illustrate the evaporation rate of the chloride deposit. Another test result on Fe with 15 mg/cm2 ZnCl2KCl in inert gas atmosphere is identical to that with 30 mg/cm2 ZnCl2KCl.

In contrast to Ni and Fe the amount of the water soluble fraction of Cr increases dramatically with increasing reaction time (Fig. 5). This is due to the formation of chromate, which is dissolved in the molten salt. The formation of oxychlorides has been also considered by thermodynamic calculations. In the p(Cl2)p(O2) diagrams for Cr they are found to be stable at very high p(O2)p(Cl2) ()1).

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Fig. 13. Left: SEM micrograph of pure Cr after reaction (120 h) beneath molten ZnCl2KCl salt mixture (15 mg/cm2) in Ar16 vol% O2 at 320 C showing chromium oxide crystals grown on the chloride melt. The image was taken from the inner part of the corrosion layer. Right: Metallographic cross-section of the same sample showing chromium oxide and chromium chloride inside the chloride melt.

4. Discussion TG tests were carried out on pure Fe, Ni and Cr while varying the amounts of chloride deposit and p(O2). Both lead to increased mass gain. For Fe a higher p(O2) yields a reduction of the incubation phase and a higher gradient during the linear stage. A larger amount of chloride deposit causes a longer incubation time. In comparison to pure oxidation the corrosion beneath molten chloride deposits is aggravated and accelerated. As this deposit acts as a chlorine source processes that release chlorine should be discussed. Thermodynamic calculations show that at the top of the salt melt layer ZnCl2 will be oxidised at 320 C and 8 vol% O2 with Ptotal = 1 bar (reaction (1)) during the initial part of the corrosion process when the chlorine partial pressure is low (Fig. 14). ZnCl2 0.5O2 ZnO Cl2
4

But as the reaction takes place a p(Cl2) of about 2 10 bar will be established at these conditions. This in turn prevents the KCl compound from oxidation. But at the metal/salt melt interface the established p(Cl2) allows the formation of iron chloride (reaction (2)) because the p(O2) is very low at inner parts of the chloride melt. Fe Cl2 FeCl2 2 The formation of iron chloride could be conrmed by SEM observations. When iron chloride diuses outward to areas ruled by a higher p(O2) iron chloride may be oxidised to hematite according to reaction (3): 2FeCl2 1.5O2 Fe2 O3 2Cl2 3 Cl2 may diuse back to the substrate/salt melt interface acting as new chlorine source for subsequent iron chloride formation. A catalytic cycle is accomplished since no chlorine will be consumed. The stability elds of iron chloride and iron oxide are illustrated in the phase diagram (Fig. 15).

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2
ZnCl2(s) log10(p(Cl2)) (bar) -20 ZnO(s)

-40

Zn(s)

KCl(s)

K2O(s2) -60 -60 -40 log10(p(O2)) (bar) -20

K2O2(s) 0

Fig. 14. Superimposed phase diagram of the system KCl2O2 and ZnCl2O2 at T = 320 C. The oxygen partial pressure of the atmosphere (here corresponding to 8 vol% O2) is indicated with 1. At the salt melt/gas atmosphere interface ZnCl2 may be oxidised to ZnO releasing chlorine. The established p(Cl2) is about 2 104 bar (line 2). The p(Cl2) is high enough to prevent KCl from oxidation. Calculated with FactSage [12].

1
FeCl2(s)

FeCl3(liq)

log10(p(Cl2)) (bar)

-20

-40

Fe(s3)

Fe3O4(s)

Fe2O3(s3)

-60 -60 -40

log10(p(O2)) (bar)

-20

Fig. 15. Phase diagram of the system FeCl2O2 at T = 320 C. The chlorine partial pressure established by reaction (1) at 8 vol% O2 is indicated with 1. Close to the metal/salt melt interface iron chloride is stable. Close to the salt melt/gas atmosphere interface hematite is stable. Calculated with FactSage [12].

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In comparison to the results for Fe the mass gains taken from the TG tests with Ni and Cr indicate that the rate of oxide formation for Ni and Cr is signicant lower. But the amount of the chlorides formed after some days of reaction do not deviate very much for the three elements. The amount of iron chloride formed decreases after 48 h of corrosion, while the formation of nickel chloride and chromium chloride continuous steadily. Especially the amount of chromium chloride increases drastically after 48 h. It seems to be obvious that in the case of iron the formation of iron oxide is predominated. For Ni and Cr the oxide formation is less pronounced. A reason for this is given by the phase diagrams for the systems NiCl2O2 and CrCl2O2 (Figs. 16 and 17). A comparison with the phase diagram for FeCl2O2 shows that the stability eld of the metal chlorides reaches to a higher p(O2) value at p(Cl2) = 2 104 bar in the case of Ni than in the case of Fe and Cr. Therefore the stability eld for NiO at p(Cl2) = 2 104 bar is limited to high P(O2) values. This might be an explanation for the low rate of NiO formation but it does not explain the high rate of chromium chloride formation and relatively low rate of Cr2O3 formation. One possible reason may be that the diusion of chromium chloride is inhibited more. Thus an enrichment of chromium chloride after a longer reaction time might be possible. A reason might be found by comparison of the phase diagram FeCl2ZnCl2KCl versus NiCl2ZnCl2KCl and CrCl3ZnCl2KCl (Figs. 1820). It shows that the solubility of FeCl2 in the molten ZnCl2KCl is higher than the solubility of CrCl3 or NiCl2 in that melt. Since metal chlorides are more mobile in liquid form the higher solubility of FeCl2 in ZnCl2KCl may be the reason for the higher
0

1
NiCl2(s)

log10(p(Cl2)) (bar)

-20

Ni(s)

NiO(s2)

-40

-60 -60 -40

log10(p(O2)) (bar)

-20

Fig. 16. Phase diagram of the system NiCl2O2 at T = 320 C. The chlorine partial pressure established by reaction (1) at 8 vol% O2 is indicated with 1. At this p(Cl2) NiO will be formed at the outermost part of the chloride melt, close to the salt melt/gas atmosphere interface, only. Calculated with FactSage [12].

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1
CrCl3(s)

log10(p(Cl2)) (bar)

-20
CrCl2(s)

Cr2O3(s)

-40
Cr(s)

-60 -60 -40

log10(p(O2)) (bar)

-20

Fig. 17. Phase diagram of the system CrCl2O2 at T = 320 C. The chlorine partial pressure established by reaction (1) at 8 vol% O2 is indicated with 1. Calculated with FactSage [12].

FeCl2
0.9

0.1

0.8

0.2

Fe C l2 + FeK Cl 3

0.7

0.3

0.6

0.4

LIQ UID +

0.5

0.5

0.4

0.6

LIQUID + FeK 2Cl4 + Fe KCl3

0.3

0.7

LIQUID + FeCl2
0.2

0.8

LIQUID + ZnK2Cl4 + FeK2Cl4

0.1

0.9

ZnK2Cl4 + KCl + FeK2Cl4

LIQUID
0.6 0.5 0.4 0.3 0.2 0.1

KCl

0.9

0.8

0.7

mole fraction

ZnCl2

Fig. 18. Phase diagram of the system FeCl2KClZnCl2 at T = 320 C. It shows that about 1015 mol% FeCl2 can be dissolved in a liquid KClZnCl2 melt near the eutectic composition. Calculated with FactSage [12].

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693

NiCl2
0.9

0.1

0.8

0.2

0.7

0.3

0.6

0.4

NiCl2 + ZnK2Cl4 + NiKCl3

0.5

0.5

l2+ ZnK2Cl

0.4

0.6

LIQUID + NiC

0.3

0.7

0.2

0.8

LIQUID + NiCl2
0.9

ZnK2 Cl4 + NiKCl3 + KCl LIQUID + ZnK2 Cl4

0.1

KCl

0.9

0.8

0.7

0.6

0.5

0.4

0.3

0.2

0.1

mole fraction

ZnCl2

Fig. 19. Phase diagram of the system NiCl2KClZnCl2 at T = 320 C. Almost no NiCl2 can be dissolved in a liquid KClZnCl2 melt near the eutectic composition. Calculated with FactSage [12].

CrCl3
0.9

0.1

0.8

0.2

0.7

0.3

0.6

0.4

0.5

0.5

KC l4 +

0.4

Cl 4

0.6

K2C

CrCl3 + Z nK

+ Zn

0.3

0.7

Cr C l

0.2

0.8

LIQUID +

0.1

0.9

LIQUID + CrCl3

KCl

0.9

0.8

0.7

0.6

0.5

0.4

0.3

0.2

0.1

mole fraction

ZnCl2

Fig. 20. Phase diagram of the system CrCl3KClZnCl2 at T = 320 C. Almost no CrCl3 can be dissolved in a liquid KClZnCl2 melt near the eutectic composition. Calculated with FactSage [12].

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rate of oxide formation in the case of iron and the lower one in the case of Cr and Ni, because less NiCl2 and CrCl3 may diuse outward to the outer part of the melt, where oxidation to oxides is possible due to higher p(O2). Therefore the solubility of the metal chloride formed during corrosion of samples covered by chloride melts is responsible for enhanced corrosion. 5. Conclusions Corrosion tests have been carried out on pure Fe, Cr and Ni covered by a 50 mol% ZnCl250 mol% KCl deposit. Results taken from TG tests yield enhanced mass gain at a relatively low temperature (320 C), especially when the amount of oxygen or salt deposit is increased. The formation of protective oxide layers can be excluded. Corrosion of Fe results in higher mass gain than corrosion of Ni and Cr. The three dierent corrosion stages that could be observed on Fe [11] (incubation phase, a linear stage, logarithmic or parabolic stage) are not discernible on TG tests carried out on Ni and Cr. Thermodynamic calculations show that iron chloride is soluble in molten KCl ZnCl2 near the eutectic compositions, while chromium chloride and nickel chloride have a very limited solubility in molten KClZnCl2. Thus the outward diusion of the NiCl2 and CrCl3 components is more restricted while FeCl2 diuses easily to outer parts of the salt melt layer and will be oxidised there due to higher p(O2). Thus we conclude that the solubility of metal chloride in molten KClZnCl2 leads to a higher diusion rate resulting in a higher oxidation rate. Therefore the solubility of metal chloride in the molten salt inuences the extent of corrosion of each metal. In conclusion, more sophisticated solubility studies will be carried out in the future to understand the eect of gases like HCl and H2O on the metal solubility. The studies have shown that even chromium undergoes rapid solubility as chromate in the melt and that alloy/coating development for water wall and superheater application should try to focus on low chromium materials and using other protective elements like Al and Si instead. Acknowledgment This work is part of the OPTICORR project, which is supported by the European Commission.

References
[1] M. Spiegel, Molten Salt Forum 7 (2003) 253. [2] G. Sorrell, Mater. High Temp. 14 (3) (1997) 207. [3] P. Kofstad, High Temperature Corrosion, Elsevier Applied Science Publishers Ltd., London, New York, 1988.

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