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Corrosion Science 59 (2012) 55–62

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Thermogravimetric studies of high temperature reactions between potassium salts


and chromium
J. Lehmusto ⇑, D. Lindberg, P. Yrjas, B.-J. Skrifvars, M. Hupa
Åbo Akademi University, Piispankatu 8, 20500 Turku, Finland

a r t i c l e i n f o a b s t r a c t

Article history: This study compares the high temperature reactions of potassium chloride (KCl) and potassium carbonate
Received 11 November 2011 (K2CO3), two salts found in fly ashes formed in biomass combustion, with both pure metallic chromium (Cr)
Accepted 20 February 2012 and chromium oxide (Cr2O3). The reactions were investigated with thermogravimetric measurements and
Available online 3 March 2012
the results discussed based on thermodynamic calculations. In simple terms: potassium chloride reacted
with chromium forming potassium chromate (K2CrO4) and chromium oxide. Potassium chloride did not
Keywords: react with chromium oxide. Potassium carbonate reacted with chromium oxide, but not with chromium.
A. Molten salts
The presence of potassium is sufficient to initiate accelerated oxidation, but chloride is needed to sustain it.
B. SEM
C. High temperature corrosion
Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction chlorine gas (Eq. (1)) [15]. Because the formation of molecular
chlorine gas is thermodynamically unfavourable in the presence
High temperature corrosion is a problem that often occurs in of water, another reaction hypothesis has been proposed in which
both biomass and waste combustion [1–3]. The combination of a hydrogen chloride (HCl) is formed instead of chlorine gas (Eq. (2))
high alkali metal content, the presence of chlorine-containing com- [16]. The formation of HCl is favoured over the formation of molec-
pounds, and a low sulfur content is responsible for the corrosive ular chlorine gas at water vapor levels above 1 ppm (Fig. 1). The cal-
nature of biomass ashes in high temperature combustion [4–7]. culated partial pressures of Cl2 and HCl for the Cr2O3–K2CrO4
To prevent or reduce corrosion, boilers are operated at lower steam transition as a function of H2O at 500 °C and p(O2) = 0.21 bar has
temperatures, and built of higher quality steels. Alloying with been performed using Factsage 6.2 [17]. The thermodynamic calcu-
chromium is known to improve steel by encouraging the formation lations and thermodynamic data used in the calculations are dis-
of a protective oxide layer consisting of a corundum-type solid cussed in detail in Section 2.3.
solution (Cr, Fe)2O3. In biomass combustion, the accelerated oxida-
tion of superheater tubes at elevated temperatures is attributed 2Cr2 O3 ðsÞ þ 8KClðsÞ þ 5O2 ðgÞ ! 4K2 CrO4 ðsÞ þ 4Cl2 ðgÞ ð1Þ
mainly to potassium chloride. However, recent studies have indi-
cated that potassium carbonate (K2CO3), a chloride-free potassium ðCr1x ; Fex Þ2 O3 ðsÞ þ 4KClðsÞ þ 3=2O2 ðgÞ þ 2H2 OðgÞ
salt found occasionally in fly ashes from biomass-fired boilers, may ! xFe2 O3 ðsÞ þ 2ð1  xÞK2 CrO4 ðsÞ þ 4HClðgÞ ð2Þ
be a factor contributing to accelerated oxidation [8–10].
The reactivity of alkali chlorides, in particular KCl, towards stain- The reactivity of potassium carbonate (K2CO3) has been less well
less steels has been extensively studied, but there are few in-depth explored than that of potassium chloride. The oxidation of metallic
analyses of the role of alkali chlorides in the accelerated oxidation of chromium has been investigated in the presence of molten carbon-
pure metallic chromium [11–14]. Although the details of the reac- ates [18–20], but mostly in terms of the reactivity of a molten
tion mechanism remain elusive, it is generally accepted that the Li2CO3/K2CO3 mixture in molten carbonate fuel cells (MCFCs) e.g.,
reaction proceeds via intermediates, such as alkali chromates, like [21]. In these systems, only Li2CO3 has been reported to cause accel-
Na2CrO4 or K2CrO4 [11,15,16]. The initiation phase of the reaction erated oxidation. However, it has been suggested that, during the
occurs between the alkali chloride and the protective chromium combustion of biomass, the reaction between potassium carbonate
oxide, forming an alkali chromate and, under dry conditions, and the protective chromium oxide is analogous to the reaction be-
tween potassium chloride and chromium oxide: the protective
⇑ Corresponding author. Tel.: +358 40 54 65 393. oxide layer is destroyed because of the formation of chromate by
E-mail addresses: juho.lehmusto@abo.fi (J. Lehmusto), daniel.lindberg@abo.fi
potassium (Eq. (3)) [8]. It should be borne in mind that, unlike
(D. Lindberg), patrik.yrjas@abo.fi (P. Yrjas), bengt-johan.skrifvars@topanalytica.com potassium chloride and potassium carbonate, potassium chromate
(B.-J. Skrifvars), mhupa@abo.fi (M. Hupa). is not found in fly ashes, but it forms as an intermediate in the high

0010-938X/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2012.02.013
56 J. Lehmusto et al. / Corrosion Science 59 (2012) 55–62

2. Experimental method
Cl2(g)
-3 HCl(g) 2.1. Sample preparation
log p(i) / bar [i = HCl, Cl2]

-4 The powder reaction mixtures were prepared using Cr, Cr2O3,


KCl, K2CrO4, and K2CO3 with 99% min purity. The melting points
-5 (s) of the potassium salts as well as the initial melting temperatures
O3
Cr 2 (s) of binary mixtures of the potassium salts are listed in Table 1
C rO 4
-6 K2 [13,25–27]. The temperatures for the KCl + K2CO3 and KCl + K2CrO4
Cr2O3(s) mixtures are the initial melting temperatures, which do not de-
-7 K2CrO4(s) pend on the composition. The melting point of the K2CO3 + K2CrO4
mixture is composition dependent, but the minimum value is
788 °C. To produce the mixtures, the reagents were weighed and
-8
mixed directly in an alumina crucible used as the sample holder
in the TG/DTA runs. The sample mass varied between 9 and
-9 -8 -7 -6 -5 -4 -3 -2 -1 24 mg. The Cr, KCl, and K2CO3 were sieved, and the fractions con-
log p(H2O) / bar sisting of particles of diameter 125–297 lm were used, whereas
the Cr2O3 consisted mostly of particles with a diameter of around
Fig. 1. Calculated partial pressures of hydrochloric acid and chlorine as functions of 300 nm. The particle size of the K2CrO4 varied roughly between
the partial pressure of water for the transition between Cr2O3 and K2CrO4 as the 50 and 200 lm. In all the binary mixtures, the mole ratio of the re-
main condensed chromium species. Temperature is 500 °C, p(O2) = 0.21 bar, and agents was 1:1, and in the ternary mixtures, 1:1:1, if not stated
solid KCl is stable together with chromium compounds.
otherwise. The reagents were also run individually as references.
temperature oxidation reactions between the superheater materials
and the two other potassium salts mentioned above. 2.2. Thermogravimetric and X-ray powder diffraction analyses

Cr2 O3 ðsÞ þ 2K2 CO3 ðsÞ þ 3=2O2 ðgÞ $ 2K2 CrO4 ðsÞ þ 2CO2 ðgÞ ð3Þ The heating runs were performed using an SDT Q600 simulta-
neous TGA/DSC apparatus (TA Instruments) except for the ternary
Cr2O3 + KCl + K2CO3 mixture, which was studied with TGA/SDTA
1
Dr G ð700 CÞ ¼ 238 kJ mol 851e (Mettler Toledo). Individual reagents as well as mixtures were
heated to 700 °C with a heating rate of 2 °C min1 (Fig. 2). All runs
It has been proposed that chromate formation is a key factor in
were executed in dry synthetic air (80% N2/20% O2) with a flow rate
the carbonate-induced high temperature oxidation of chromium
of 100 ml min1. The purity of both gases was 5.0 (99.999%). When-
[18]. When the reactivities of (Li, K)2CO3 and (Li, K)2CrO4 were com-
ever possible, the samples were examined after the run with a scan-
pared, the mass of chromium increased to nearly the same extent
ning electron microscope (LEO 1530 Gemini) coupled with an X-ray
with the mixed carbonate or with the mixed chromate. It has been
detector (Thermo Scientific UltraDry). Some of the samples were
found that the presence of molten carbonate is essential for the
also examined with an optical microscope (Leica Wild MZ 8) com-
oxidation of Cr(III) (in Cr2O3) to Cr(VI) (in chromates) [22]. The for-
bined with an external light source (Intralux 6000-1).
mation of chromates in molten carbonates begins with the forma-
The X-ray powder diffraction (XRPD) measurements were per-
tion of peroxide ions, which react further with the chromium oxide
formed using Philips X’Pert Pro MPD. It has a Bragg–Brentano dif-
to form chromates [23].
fraction geometry and it was operated with monochromated CuKa
In our previous paper, the capability of potassium carbonate to
radiation at 40 kV/50 mA. The primary X-ray beam was collimated
accelerate the oxidation of an austenitic stainless steel was re-
with a fixed 0.25° divergence slit and a fixed 10 mm mask. A 0.25°
ported [10]. The rate of corrosion was studied from the cross sec-
fixed anti-scatter slit and a programmable receiving slit set at
tions of coupons, which were exposed to the salt for one week.
0.30 mm were used in the diffracted beam side prior to the propor-
With this technique, however, the reactions involved could not
tional counter. Due to the small amount of samples all samples
be studied in detail. Thermogravimetry combined with differential
were measured using silicon wafer as a sample holder. The used
thermal analysis (TG/DTA) has proven to be a useful and suitable
holder has on diffraction peak at approximately 33°. The measur-
tool to study the behavior of a reaction mixture as a function of
ing range of 10–50° and a scanning speed of 0.04°/4s were used.
time, for example. This was done in our earlier paper, where the
In order to determine the instrumental function of the instrument
reaction between potassium chloride and chromium was studied
a silicon standard was measured. The samples were ground gently
in terms of chromate formation and its role in the oxidation chro-
prior to the measurements. The measured diffractograms were
mium [24]. Some of the findings of the previous paper [24], the role
analyzed using Rietweld refinement technique with MAUD pro-
of potassium chromate (K2CrO4) for example, are vital for the inter-
gram. The crystal structures of the studied materials were re-
pretation of the findings reported in this paper, and are referred to
trieved from the ICSD database. For the phase identification and
for comparison.
comparison the Philips X’Pert HighScore program equipped with
This work has two main purposes. The first is to shed more light on
Powder Diffraction File (PDF) database was used.
the complex chemistry of the reaction between potassium chloride
and chromium and that between potassium chloride and chromium
oxide under oxidizing conditions at high temperatures. The second is 2.3. Thermodynamic calculations
to obtain information about the tendency of potassium carbonate to
react with chromium or chromium oxide. The role played by potas- Thermodynamic equilibrium modeling was used to predict the
sium chromate in these reactions was of special interest. Reactions stable products in the experiments. The data sources used in the
of various combinations of these reagents in the form of powders were calculations are presented in Table 2 [28–35]. The computational
studied using thermogravimetry combined with differential thermal methods involved in calculating multiphase multicomponent
analysis (TG/DTA). In this work, all the experiments were performed thermodynamic chemical equilibria are based on Gibbs energy
under dry conditions, and the effect of water vapor was not considered. minimization [36].
J. Lehmusto et al. / Corrosion Science 59 (2012) 55–62 57

Table 1 of the solution phases that give a global minimum of the total Gibbs
Melting temperatures of pure reagents and binary mixtures. energy of the system.
Reagent Melting temperature Mixture Melting temperature The Gibbs energy is related to the enthalpy H, the entropy S, and
(°C) (°C) the heat capacity Cp in the following manner:
KCl 771 [26] KCl + K2CO3 631 [26] Z T  Z T 
K2CO3 901 [25] KCl + K2CrO4 650 [13] C p ðTÞ
GðTÞ ¼ DH298 þ C p ðTÞdT  T  S298 þ dT ð6Þ
K2CrO4 980 [13] K2CO3 + K2CrO4 788 [27] 298 298 T
The values of DH298, S298, and Cp(T) are often stored in thermo-
dynamic data compilations. Alternatively, the corresponding Gibbs
energy functions can be given directly.
The calculations were performed using the thermodynamics
700 125 software package FactSage version 6.2 [17]. The calculations for
the stoichiometric condensed phases and the gas phase were based
600
120 on the FACT53 database.

Relative mass (%)


Temperature ( C)

500 The elements C–Cr–K–N–O were considered in the calculations.


o

115 All compounds found in the database were incorporated, with the
400 exception of those involving nitrogen: N2 was the only nitrogen
110 compound included. It is well known that thermodynamic equilib-
300 u re
e ra t rium modeling does not adequately predict nitrogen chemistry un-
mp
Te der combustion conditions, nor was the nitrogen chemistry of
200 105
interest in the present study. The original sources for the thermo-
100 Relative mass dynamic data of the main predicted condensed and gaseous spe-
100
cies are given in Table 2 [28–35]. The thermodynamic data for
50 100 150 200 250 300 K2Cr2O7 is not available in the standard FACT53 database but
Time (min) was included in the calculations. The values for DH298 and S298
for K2Cr2O7 are taken from Wagman [33], Cp from the HSC chemis-
Fig. 2. Typical plot of the sample mass relative to the initial weight of the sample, try database [32] and the transition temperatures and transition
and the heating sequence as functions of time.
enthalpies from Nolte et al. [31].
The modeling also considered a liquid phase consisting of
K2CO3, K2CrO4, and K2Cr2O7. The liquid phase is an ionic phase con-
Table 2 sisting of one cation, K+, and three anions, CO2 2 2
3 , CrO4 , and Cr2 O7 .
Source for thermodynamic data of relevant A modified quasichemical model [26,37] was used to describe the
species in thermodynamic predictions. All
thermodynamic properties of the liquid phase. The melting proper-
thermodynamic data are accessed through
the thermodynamic software package Factsage ties of the K2CO3–K2CrO4–K2Cr2O7 mixtures have been described in
[17]. part by Lindberg et al. [38], and a detailed list of the solution
parameters will be published elsewhere. The binary interactions
Compound Reference
for the K2CO3–K2Cr2O7 and K2CrO4–K2Cr2O7 systems are ideal
Cr(s) [28]
and the binary interactions for the K2CO3–K2CrO4 system shows
Cr2O3(s) [29]
K2CrO4(s1, s2, l) [30] minor deviation from ideality.
K2Cr2O7(s,l) [31–33] Predictions were made for all the experimental mixtures with a
KCl(s,l,g) [30] given composition, usually a 1:1 mol ratio, unless otherwise stated.
K2CO3(s1,s2, l) [34,35] The experiments were run at 500 and 700 °C, and the gas compo-
HCl(g) [34]
Cl2(g) [34]
sition was set by adding air to achieve a p(O2) = 0.2 bar at the final
O2(g) [34] equilibrium. The results are discussed in the following section.
H2O(g) [34]
N2(g) [34]
CO2(g) [34] 3. Results and discussion

The results have been organized according to the sample type.


The classical method for calculating phase equilibria from equi- The reactions studied were compared with the thermodynamic
librium constants is not suitable for large multicomponent multi- equilibrium calculations performed with FactSage version 6.2 to
phase systems. The true chemical equilibrium can be calculated verify the thermodynamic possibility of the observed reactions
by considering the Gibbs energy of all phases and minimizing the and to support the findings. The calculations are summarized in
total Gibbs energy G of the system. Here, G can be calculated either Table 3. The column subchapter indicates, in which subchapter
from the chemical potential (Gi , li) of each component i, by products are discussed in more detail. Some of the calculations
X have been reported earlier in [24]. The term ‘‘relative mass’’ will
G¼ ni Gi ; ð4Þ
i
be used when the weight changes of the samples are discussed.
If not stated otherwise, the relative masses are relative to the initial
where ni is the amount of component i, or by weight of each sample at the beginning of every test, so that every
X test starts with a relative mass of 100%.
G¼ N/ G/m ð5Þ
/
3.1. Individual reagents
where N / is the amount of a phase, and G/m is the Gibbs energy of
the phase. For a given set of constraints, such as fixed values of P, When Cr or Cr2O3 was examined, no changes were detected
T, and the overall composition, the Gibbs energy minimization algo- either in the mass (the TG curve) or in the temperature difference
rithms find the amounts of the various phases and the composition between the sample and the reference (the DTA curve). According
58 J. Lehmusto et al. / Corrosion Science 59 (2012) 55–62

Table 3 roughly between 50 and 350 °C is due to the normal baseline drift
Calculated products for all samples at 500 °C and 700 °C under an O2 partial pressure of the temperature difference curve. The relative effect of the base-
of 0.2 bar.
line becomes bigger when low heating rates are used.
Sample Temperature Main product(s) Subchapter
(°C) 3.2. Binary systems
Cr 500–700 Cr2O3(s) 3.1b
Cr2O3 500–700 Cr2O3(s) 3.1b 3.2.1. Binary salt systems
KCl 500–700 KCl(s) 3.1b
K2CrO4 500–700 K2CrO4(s) 3.1b
When the K2CO3 + K2CrO4 mixture was studied, in addition to
K2CO3 500–700 K2CO3(s) 3.1 the K2CrO4 phase transformation signal, a broad endothermic
KCl + K2CrO4 500 KCl(s), K2CrO4(s) 3.2b DTA signal was observed, which peaked at approximately 594 °C.
KCl + K2CrO4 700 K2CrO4(s), (KCl/ 3.2b However, the mass of the sample remained unchanged, suggesting
K2CrO4)(l)
that the DTA signal resulted from the formation of a K2CO3 + K2-
KCl + K2CO3 500 KCl(s), K2CO3(s) 3.2
KCl + K2CO3 700 K2CO3(s), (KCl/K2CO3)(l) 3.2 CrO4 solid solution. No melt was observed, since the test tempera-
K2CO3 + K2CrO4 700 (K2CO3/K2CrO4)(ss) 3.2 tures were below 788 °C, the lowest initial melting temperature
Cr + KCl 500–700 KCl(s), Cr2O3(s), (KCl/ 3.2b [27].
K2Cr2O7)(l) Melting was observed with the KCl + K2CrO4 mixture starting at
Cr + K2CrO4 500–700 K2Cr2O7(l) 3.2b
653 °C, which is close to 650 °C, the temperature reported in the
Cr + K2CO3 500–700 K2CrO4 (s) 3.2
Cr2O3 + KCl 500–700 KCl(s), Cr2O3(s), (KCl/ 3.2b literature [13]. Although melting clearly occurred in the mixture,
K2Cr2O7)(l) the endothermic DTA signal for the orthorhombic–hexagonal
Cr2O3 + K2CrO4 500–700 K2Cr2O7(l), Cr2O3(s) 3.2b phase transformation was still detected at 669 °C [24]. The phase
Cr2O3 + K2CO3 500–700 K2Cr2O7(l)a 3.2
transition signal indicated that not all the K2CrO4 was in the mol-
Cr + KCl + K2CO3 500 KCl(s), K2CrO4(s) 3.3
Cr + KCl + K2CO3 700 K2CrO4(s), (KCl/ 3.3 ten phase; rather, it had remained partly in the solid state. The
K2CrO4)(l) mass started to decrease at the initial melting temperature, most
Cr2O3 + KCl + K2CO3 500 KCl(s), (KCl/K2Cr2O7)(l) 3.3 likely due to evaporation, and the relative mass had decreased by
Cr2O3 + KCl + K2CO3 700 (KCl/K2Cr2O7)(l)a 3.3 2% by the end of the run.
a
Cr2O3(s) as trace product. The KCl + K2CO3 mixture was studied in two different mole ra-
b
Reproduced from [24]. tios: 1:1 and 2:1; however, the composition did not influence the
behaviour of the samples. In both cases, melting was observed at
635 °C, which agrees well with the calculated initial melting tem-
perature, 631 °C [26]. The mass started to decrease at the melting
to the DTA curve, melting did not occur with KCl, K2CO3, or K2CrO4 temperature, most likely due to evaporation, and the relative mass
in the temperature range studied. By the end of the run, the rela- had decreased by approximately 2% by the end of the run (Fig. 4).
tive masses of KCl and K2CO3 had decreased by 1% and 3%, respec- The observations were in good agreement with the thermody-
tively. In the case of KCl, this was caused by slight evaporation of namic equilibrium calculations (Table 3). No new species were
the salt, and in the case of K2CO3, by the evaporation of physically formed, and the calculations also predicted the physical changes
bound water. With K2CrO4, an endothermic signal occurred in the observed: the formation of a K2CO3 + K2CrO4 solid solution, and
DTA curve at 670 °C, indicating the orthorhombic–hexagonal phase the melting of both the KCl + K2CrO4 and KCl + K2CO3 mixtures.
transformation, which has been reported in the literature (Fig. 3) Both melting temperatures, 653 °C for the KCl + K2CrO4 mixture
[24,39]. According to the thermodynamic equilibrium calculations and 635 °C for the KCl + K2CO3 mixture, were high compared to
(Table 3), oxidation of chromium should occur during heating, the steam temperatures currently in use. Accordingly, the melt for-
hence increasing the relative mass, but this was not observed. mation of these binary salt mixtures is unlikely to be the primary
Apparently, the oxidation of chromium occurred either so slowly cause of the initiation of accelerated oxidation of the steels in a
or in such small amounts that it made no observable change in biomass-fired steam boiler.
the TG curve. The soft wave-like shape of some of the DTA curves
3.2.2. Binary chromium/salt systems
The DTA/TG graphs for the Cr + KCl and Cr + K2CrO4 mixtures
were presented in a previous paper, along with a detailed analysis
Relative mass (%)
115 o
Temperature difference ( C) 2 of the results [24], so only a brief discussion is included here. The
relative mass of the Cr + K2CrO4 mixture increased by 2% due to
Temperature difference ( C)

110 the formation of chromium oxide and potassium dichromate


o
Relative mass (%)

1
(K2Cr2O7).
105
When the results for three Cr + KCl mixtures with different
0 mole ratios (1:1, 1:2, 5:1) were compared, similarities could be
100
found among the mass curves and among the DTA curves. For each
95 mixture, the DTA curve consisted of two distinct exothermic reac-
-1 tion signals, which peaked at around 535 °C and 660 °C (Fig. 5). A
90 * mass increase was associated with each of the exothermic reac-
Exo tions; the corresponding slopes were different. The two distinct
85 -2
Endo
exothermic signals, each associated with a different mass increase
rate, suggested that the reaction consisted of two separate reac-
100 200 300 400 500 600 tions, as noted earlier [40]. During the first stage, the protective
o
Temperature ( C) oxide layer on the original chromium particle is destroyed through
potassium chromate formation, and once the surface with its pro-
Fig. 3. The sample mass relative to the initial weight of the sample (solid line) and
DTA curves (dashed line) for K2CrO4 as functions of temperature in synthetic air
tective properties is removed, the second stage of the reaction pro-
with a heating rate of 2 °C min1. The asterisk () indicates the endothermic phase ceeds via accelerated oxidation, i.e., direct exposure of chromium
transition at 670 °C [24]. to potassium chloride. It is likely that, during the first mass in-
J. Lehmusto et al. / Corrosion Science 59 (2012) 55–62 59

(Fig. 7). When heating was continued to 800 °C in another run,


Relative mass (%)
115 o
Temperature difference ( C) the relative mass increased by 2%, but the increase came to an
1 end before heating was completed. However, SEM revealed traces

Temperature difference ( C)
o
110 of a compound containing potassium, chromium, and oxygen; it
Relative mass (%)

0 appeared yellow when examined with an optical microscope. It


105
was identified to be potassium chromate (K2CrO4) by the XRPD
100
measurements.
-1
Apart from the absence of liquid K2Cr2O7 as a product of the reac-
95 tion between chromium and potassium chloride, the observations
-2 were in good agreement with the thermodynamic equilibrium cal-
90 culations (Table 3). According to the calculations, K2Cr2O7 should
-3 have been formed as the main product of the reaction between Cr
85
Exo
*
and KCl, while K2CrO4 should have been the product of the reaction
Endo
between Cr and K2CO3. However, although the formation of both
100 200 300 400 500 600 products is thermodynamically favoured, only traces of each species
o
Temperature ( C) were found. This was likely due to kinetic factors.
Fig. 4. The sample mass relative to the initial weight of the sample (solid line) and
DTA curves (dashed line) for the KCl + K2CO3 mixture (mole ratio 1:1) as functions 3.2.3. Binary chromium oxide/salt systems
of temperature in synthetic air with a heating rate of 2 °C min1. The asterisk ()
The reactions of both the Cr2O3 + KCl and Cr2O3 + K2CrO4 mix-
indicates the endothermic initial melting at 635 °C.
tures have already been reported, along with a detailed analysis
of the results [24], so only a brief discussion is included here. In
crease, small amounts of potassium chromate are formed, after the reaction between Cr2O3 and KCl, no mass or temperature
which chromium reacts to chromium oxide during the more rapid changes could be observed, but traces of K2CrO4 were detected
mass increase. For the three mixtures, the mass increase during the with SEM-EDX. A repetition test with a mole ratio of 2:1 (2 mol
second stage was greatest in the Cr + KCl mixture with a mole ratio KCl for one mole Cr2O3) was carried out, but no changes in mass
of 5:1. This supports the assumption that the second exothermic or in temperature difference could be observed. In the reaction be-
reaction involves the oxidation of chromium. The Cr2O3 produced tween Cr2O3 and NaCl, an alkali salt very similar to KCl, it has been
consisted of separate crystals forming a continuous, yet porous reported that significant amounts of sodium chromate (Na2CrO4)
layer (Fig. 6). The porosity of the layer may well explain the ab- were formed [44]. The tests in reference [44] were carried out un-
sence of protective properties, which in turn means that the parti- der normal ambient humidity, which could explain the elevated
cles are converted into Cr2O3 at a higher rate. Based on the 2:1 reactivity of the mixture, while the tests in this work were per-
potassium-to-chromium ratio obtained from the SEM/EDX analy- formed in synthetic air. In the case of Cr2O3 + K2CrO4, the relative
sis, K2CrO4 was detected, supporting the hypothesis that it is mass increased by 2%, which was explained in terms of the forma-
formed as an intermediate in the reaction. Chromate ion was also tion of K2Cr2O7 [24].
identified with ion chromatography (IC), which has been used ear- The mass of the Cr2O3 + K2CO3 mixture decreased in two stages:
lier for chromate ion identification e.g. [41]. Due to the equilibrium the first decrease, occurring at the beginning of the test, was attrib-
of chromate ðCrO2 2
4 Þ and dichromate ðCr2 O7 Þ ions in water solu-
uted to the evaporation of physically bound water (Fig. 8). The sec-
tions, it is possible to only confirm the presence of a chromate, ond decrease started at around 560 °C and ended with a decrease
but not to conclude, whether one or both of the aforementioned of 6% relative to the mass remaining after the evaporation of phys-
chromates have formed in the reaction [42,43]. ically bound water. Although no unambiguous signal could be ob-
In contrast to the behaviour observed for the Cr + KCl mixtures, served in the DTA curve at 560 °C, the endothermic signal for the
no changes were detected in either the mass curve or in the DTA orthorhombic-hexagonal phase transformation of K2CrO4 was ob-
curve for Cr + K2CO3 mixtures with mole ratios 1:1 and 2:1 served at 670 °C.
The formation of K2CrO4 in the reaction between Cr2O3 and
K2CO3, predicted by Eq. (3) [8], is suggested by the endothermic
signal for the orthorhombic–hexagonal phase transformation
Relative mass (%)
115 o 2
Temperature difference ( C)
Temperature difference ( C)
o

110
Relative mass (%)

1
105

100 ** 0

95
* -1
90
Exo
85 -2
Endo

100 200 300 400 500 600


o
Temperature ( C)

Fig. 5. The sample mass relative to the initial weight of the sample (solid line) and
DTA curves (dashed line) for the Cr + KCl mixture (mole ratio 1:1) as functions of
temperature in synthetic air with a heating rate of 2 °C min1. The asterisks indicate Fig. 6. The porous Cr2O3 formed on the surface of a single chromium particle in the
the exothermic reactions at 535 °C () and 660 °C (). Cr + KCl-mixture heated to 700 °C.
60 J. Lehmusto et al. / Corrosion Science 59 (2012) 55–62

1
Relative mass (%) Dr G ð700 CÞ ¼ 161 kJ mol
115 o
Temperature difference ( C)
2
The accelerated oxidation of chromia protected steels appears to

Temperature difference ( C)
occur in two consecutive stages, each of which requires both potas-

o
110
Relative mass (%)

1 sium and chloride. In the first stage, the protective chromium oxide
105 layer is destroyed through a reaction with potassium, from either
potassium chloride or potassium carbonate, leading to the forma-
100 0
tion of potassium chromate (K2CrO4) and/or potassium dichromate
(K2Cr2O7). The condition dependency of dichromate formation
95
-1 could not be solved within the scope of this study. The role of the
90 formed chromates is most likely the lowering of the initial melting
Exo
temperature of the mixtures rather than sustaining either the deple-
85 -2 tion of the protective chromium oxide layer or the oxidation of the
Endo
exposed chromium. This is supported by the scarce reactivity of
100 200 300 400 500 600 K2CrO4 with chromium at temperatures relevant to present-day
o
Temperature ( C) biomass combustion. What comes to the oxide layer destruction,
if an adequate amount of K2CrO4 is present, it could consume the
Fig. 7. The sample mass relative to the initial weight of the sample (solid line) and Cr2O3 layer and destroy the layer’s protective properties [24]. How-
DTA curves (dashed line) for the Cr + K2CO3 mixture (mole ratio 1:1) as functions of ever, the formation of K2CrO4 in such amounts has not been re-
temperature in synthetic air with a heating rate of 2 °C min1.
ported. It has also been reported that in the reaction between KCl
and a 304-type austenitic steel, K2CrO4 could be detected only dur-
observed with TG/DTA. An indication of the presence of K2CrO4 was ing the first hour of the reaction [16]. This supports the hypothesis
also detected with SEM-EDX (Fig. 9): in the EDX spectrum the that K2CrO4 is not the main active component in sustaining the
potassium-to-chromium ratio was 2:1, and the presence of the accelerated oxidation. For accelerated oxidation to continue, the
chromate ion was verified with IC. A total weight decrease of about presence of chloride is essential: during the second stage, a reaction
9% would indicate complete conversion into K2CrO4. occurred between chloride and the exposed chromium. However,
Indications of potassium dichromate formation could be ob- the reaction could not progress to the second stage in the presence
served in the reaction between Cr2O3 and K2CrO4 as well as in that of potassium carbonate, that is, in the absence of chloride.
between Cr2O3 and K2CO3, although no undisputed identification
could be obtained. The list of products detected from the reactions 3.3. Ternary systems
between Cr2O3 and the various potassium salts agreed well with
the predictions of the thermodynamic equilibrium calculations When a ternary mixture containing Cr, KCl, and K2CO3 was stud-
(Table 3). Although a small amount of K2CrO4 was formed in the ied, a sharp endothermic signal was detected at the initial melting
reaction between Cr2O3 and KCl, no evidence of K2Cr2O7 formation temperature (634 °C) of the binary KCl + K2CO3 mixture. This indi-
was observed. The calculated Gibbs free energies for the reactions cated that the presence of chromium did not affect the melting
forming chromates indicated that these reactions were spontane- behaviour. At the onset of melting, the mass began to decrease
ous (Eqs. (3), (7), (8)). At 700 °C, the DG° values are 476 kJ (Eq.
(3)), 168 kJ (Eq. (7)), and 322 kJ (Eq.8):
Cr2 O3 ðsÞ þ 2K2 CrO4 ðsÞ þ 3=2O2 ðgÞ ¼ 2K2 Cr2 O7 ðlÞ ð7Þ

1
Dr G ð700 CÞ ¼ 84 kJ mol

Cr2 O3 ðsÞ þ K2 CO3 ðsÞ þ 3=2O2 ðgÞ ¼ K2 Cr2 O7 ðlÞ þ CO2 ðgÞ ð8Þ

Relative weight (%)


o
115 Temperature difference ( C) 2
Temperature difference ( C)
o

110
Relative mass (%)

1
105
*

100 0

95
-1
90
Exo
85 -2
Endo

100 200 300 400 500 600


o
Temperature ( C)

Fig. 8. The sample mass relative to the initial weight of the sample (solid line) and
DTA curves (dashed line) for the Cr2O3 + K2CO3 mixture (mole ratio 1:1) as
functions of temperature in synthetic air with a heating rate of 2 °C min1. The Fig. 9. EDX spectrum of K2CrO4 formed in the reaction between Cr2O3 and K2CO3 at
asterisk () indicates the endothermic solid state phase transition of K2CrO4. 700 °C.
J. Lehmusto et al. / Corrosion Science 59 (2012) 55–62 61

Relative weight (%) Relative mass (%)


o
Temperature difference ( C) 2 o
115 115 Temperature difference ( C)
40

Temperature difference ( C)

Temperature difference ( C)
o

o
110 110
Relative mass (%)

Relative mass (%)


1

105 105 30
0
100 100
-1 20
95 95

90 -2 90 10
Exo Exo
85 85
-3
Endo * Endo 0
100 200 300 400 500 600 100 200 300 400 500 600
o o
Temperature ( C) Temperature ( C)

Fig. 10. The sample mass relative to the initial weight of the sample (solid line) and Fig. 11. The sample mass relative to the initial weight of the sample (solid line) and
DTA curves (dashed line) for the Cr + KCl + K2CO3 mixture (mole ratio 1:1:1) as DTA curves (dashed line) for the Cr2O3 + KCl + K2CO3 mixture (mole ratio 1:1:1) as
functions of temperature in synthetic air with a heating rate of 2 °C min1. The functions of temperature in synthetic air with a heating rate of 2 °C min1.
asterisk () indicates the endothermic initial melting at 634 °C.

also formed in the experiments with the binary Cr2O3 + K2CO3 mix-
slowly, resulting in a total mass decrease of less than 2% at the end of ture. However, K2Cr2O7 was not formed in the reaction between
the test (700 °C) (Fig. 10). The partially molten Cr + KCl + K2CO3 Cr2O3 and K2CO3, suggesting that the presence of KCl and/or melt
sample could not be removed from the sample holder and studied is essential for K2Cr2O7 formation. It should be noted that the tem-
with SEM-EDX. However, observation with an optical microscope perature at which K2Cr2O7 began to form (636 °C) is above the
provided no evidence of chromate or chromium oxide formation. superheater tube surface temperatures currently in use. With this
Visual observations are based on the strong characteristic colors in mind, more attention should be paid to the formation of K2CrO4,
of the compounds; green (Cr2O3), yellow (K2CrO4), and orange which occurred at a temperature (534 °C) close to the tempera-
(K2Cr2O7). tures relevant to biomass combustion.
The mass and DTA curves for the ternary mixture were nearly The observations for the ternary Cr + KCl + K2CO3 mixture dif-
identical to those for the binary KCl + K2CO3 mixture (Fig. 4). Chro- fered from the thermodynamic equilibrium calculations because
mium remained practically unoxidized in the presence of K2CO3 K2CrO4 formation, either solid or liquid, was not detected. In the
alone (Fig. 7), but the presence of KCl caused a mass increase of case of the ternary Cr2O3 + KCl + K2CO3 mixture, the calculations
17% (Fig. 5). The formation of melt appeared to hinder the oxida- supported observations of K2Cr2O7 formation. Although K2Cr2O7
tion of chromium. This could have resulted from the very low oxy- was formed at relatively high temperatures, it is known to lower
gen partial pressures at the chromium surface: if virtually no the initial melting temperatures in mixtures with KCl and/or
oxygen could penetrate the melt to reach the surface, no oxidation K2CrO4 [45,46]. During biomass combustion, the supply of KCl via
could occur. The complex chemistry of this ternary system needs to fly ashes to deposits on the superheater tube surfaces can be con-
be studied further. Nevertheless, the formation of melt did not in sidered to be continuous. In this situation, the ability of K2Cr2O7 to
itself always accelerate the oxidation of chromium. lower the eutectic temperature might play a significant role in
The behaviour of the ternary mixture changed significantly accelerated oxidation.
when chromium was replaced by chromium oxide. The mass of
the Cr2O3 + KCl + K2CO3 mixture began to decrease at 534 °C,
although no unambiguous signal could be observed in the DTA 4. Conclusions
curve (Fig. 11). This occurred at a slightly lower temperature than
it did with the Cr2O3 + K2CO3 mixture (Fig. 8). The mass stopped At temperatures relevant or close to present-day superheater
decreasing at 636 °C, and the total decrease was approximately surface temperatures, potassium chloride reacted with chromium
7%. After this, it began increasing, reaching 95% of its initial value, forming potassium chromate as intermediate and chromium oxide
2% above the lowest mass, which was detected at 636 °C. The de- as product. Potassium chloride did not react with chromium oxide.
crease in mass was similar to that observed for the Cr2O3 + K2CO3 Potassium carbonate reacted with chromium oxide forming potas-
mixture, indicating the formation of K2CrO4. The turning point sium chromate, but it did not react with chromium.
(636 °C) for the mass was very close to the initial melting temper- The accelerated oxidation of chromia protected steels appears
ature of the KCl + K2CO3 mixture (635 °C). This suggests that the to occur in two consecutive stages. In the first stage, the protective
formation of melt changed the conditions, making them unfavour- chromium oxide layer is destroyed through a reaction with potas-
able to the formation of K2CrO4. sium, from either potassium chloride or potassium carbonate, lead-
The increase in the mass suggested that K2Cr2O7 was formed ing to the formation of potassium chromate (K2CrO4) and/or
after the melting of the mixture. The orange color observed with potassium dichromate (K2Cr2O7). For accelerated oxidation to con-
an optical microscope also supported the hypothesis that K2Cr2O7 tinue, the presence of chloride appears to be essential: during the
was formed in the reaction between Cr2O3 and K2CrO4. Unfortu- second stage, a reaction occurred between chloride and the ex-
nately, the sample had melted and could not be studied with posed metal, in the present study, chromium. However, the reac-
SEM or XRPD. In these experiments, the formation of K2Cr2O7 oc- tion could not progress to the second stage in the presence of
curred in two consecutive reactions: K2CrO4 was formed in the potassium carbonate, that is, in the absence of chloride.
reaction between Cr2O3 and K2CO3 (Eq. (3)); and the K2CrO4 then The findings clarify the role of both potassium and chloride in
reacted further with Cr2O3 to form K2Cr2O7 (Eq. (7)). The presence the accelerated oxidation of superheater tube materials, which
of KCl was not essential for the formation of K2CrO4 because it was were mimicked in this paper by pure chromium and chromium
62 J. Lehmusto et al. / Corrosion Science 59 (2012) 55–62

oxide. However, the results are not applicable as such to biomass thermochemical software and databases – recent developments, Calphad 33
(2009) 295–311.
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