Corrosion Science, Vol. 20, pp. 383 to 404 0010-938X/80/0301-383 $02.

00/0
Pergamon Press Ltd. 1980. Printed in Great Britain.

CORROSION OF AUSTENITIC STEELS IN MOLTEN

SULPHATE DEPOSITS*

A. HENDRY
Crystallography Laboratory, The University, Newcastle upon Tyne, England
and
D. J. LEES
C.E.G.B. (Midlands Region). Scientific Services Department, Ratcliffe-on-Soar,
Nottingham, England

Abstract--Thermal analysis has been used to determine the melting behavzour of alkali metal sulphate
deposits typical of those found on superheater tubes in coal-fired power station boilers. Additions
of 5-30 m/o Fes(SO4)8 to Na,SO4-K2SO~ mixtures under a simulated flue gas (N2 + 15 v/o CO, +
1 v/o O, + 0.3 v/o SOn) are shown to reduce the melting point from 820°C to below 550°C. Alkali-
iron trisulphates are formed which re-solidify on heating above 720°C by decomposition of Fe2(SO4)s
at low thermodynamic activity. It is suggested that the effect of heat flux and SO8 potential gradient
on the melting behaviour of a superheater deposit could account for the observed 'bell-shaped'
temperature dependence of corrosion rate in the range 550--750°C. Results are presented of laboratory
corrosion tests on three commercial austenitic stainless steels using a melt of composltzon 74 m/o
Na2SO4 + 20 m/o K2SO4 + 6 m/o Fe2 (SO4)a. A model is proposed for corrosion by art acid fluxing
mechanism involving refractory metal alloy elements in the steels. The model offers a quantitative
basis for prediction of fireside corrosion resistance in coal-fired boilers, and a comparison of relative
corrosion rates of a range of steels in laboratory tests, probe trials and service performance confirms
the validity of the present model.

INTRODUCTION
IN THE last 30 years a great deal o f attention has been devoted to elucidating the
mechanism o f molten deposit attack on superheater and reheater alloys in con-
ventional coal-fired steam raising plants. Today, however, alloys are being selected
for service largely on the basis o f k n o w n response to operational parameters rather
than from an understanding o f the fireside corrosion mechanism, which is still
insufficiently complete to account for differences in the innate corrosion resistance o f
austenitic alloys over the range o f service metal and gas temperatures. There is a
particular need for further work on the physico-chemical aspects o f deposit formation
and the effect o f chemical and thermal gradients on transport processes within the
melt. There are two outstanding questions in this area: (i) the effect o f oxide scale
on the tube surface on the range o f stability o f the molten deposit, and (ii) the manner
by which deposit aggressiveness, i.e. the rate o f metal solution, is affected by detailed
alloy composition, especially the presence o f refractory metals such as niobium,
tungsten or molybdenum.
Existing knowledge o f deposit chemistry has evolved from the early laboratory
studies o f Corey e t al., 1 who were amongst the first workers to identify the presence
o f alkali iron trisulphates o f the type (Na, K)aFe(SO4)3 in 'enamels' on wasted tubes
*Manuscript received 22 January 1979; in amended form 20 June 1979.
383
 384 A. HENDRYand D. J. LEES

(in the wall of a PF-fired slag tap boiler), and Cain artd Nelson 2 who related the
stability of these compounds, which originate from reaction between SOs and alkalis
released into the flue gas, to the 'bell-shaped' dependence of corrosion and tem-
perature for austenitic and ferritic superheater alloys, which has since been shown to
obtain in service for a wide range of materials, a-5
Investigations of the melting range of alkali sulphates and pyrosulphates have
been reported by Anderson and Goddard 6 and Coats et al., 7 who showed the melting
point range to be strongly dependent on both the partial pressure of SOs in the gas
phase and the relative proportions of sodium and potassium in the melt. Sulphate-
pyrosulphate-SO8 equilibria were also reported, s-x° Pyrosulphates, however, are not
considered relevant to superheater attack at normal temperatures ( > 850 K) and
potassium-to-sodium-ratios, owing to the requirement for their formation of SO.~
concentrations well above those obtained from the stoichiometric combustion of
pulverised coal. 7
The addition of iron, originating from either the ash or the tube oxide to produce
a ternary sulphate system is of great importance as the melting points can fall well
within the range of superheater and reheater metal temperatures. Such alkali iron
sulphates can in fact be readily produced in the laboratory under a synthetic flue gas
mixture catalyzed to produce a desired s e a potential. Corey and co-workers, 1 for
example, achieved this in three ways:
(i) heating stoichiometric mixtures of Feb(Sea)3 and alkali metal sulphates in sealed
ampoules (to retain SO3).
(ii) heating F%Os powder with solid solutions of sodium and potassium sulphates
in 7250 ppm sea, and
(ii) exposing oxide from heavily scaled steel to 1000 ppm and 5000 ppm SOs
after dipping in fused 75~K~SO4 + 25~Na2SO4, the higher SO3 potential pro-
ducing twice the rate of conversion of iron oxide to KsFe(SO4)s.
The potassium-to-sodium ratio for a given mole fraction of Feces was found to
have a profound effect on the reactivity of the melt, a result later confirmed by Cain
and Nelson 2 who demonstrated that a minimum melting point of 552°C occurred in
a Na3Fe(SO4)s/KsFe(SO4)s mixture between 1 : 1 and 2 : 1 molar ratio of potassium
to sodium. A depression in melting point to ca. 627°C also occurs when 12 mol~o
Fe2(SO4)s is added to K2SO4.ix
With this work in mind a ternary sodium, potassium, iron sulphate melt was
adopted for mechanistic studies of fireside corrosion in the austenitic alloys AISI
347, AISI 316 and Esshete 1250 (United Steel Company). Melts based on the sodium,
potassium, lithium sulphate system containing 70 w/o LiSO4 and melting at 530°C 12
which are often chosen for experimental convenience, were rejected as LiSO4 is not
normally found in deposits in fossil-fired boilers. This work was motivated by the
current uncertainty concerning the comparative fireside corrosion resistance of
Esshete 1250 (15Crl0Ni6MnlMo V Nb), AISI 316 (18Crl0Ni3Mo) and AISI 347
(18Crl0NiNb) steels as a result of conflicting data from probe tests, in s i t u trials
and service performance, 5 all of which are subject to error in interpretation owing to
gas and metal temperature variation and the effects of slagging and tube position
To our knowledge, no previous mechanistic investigations have been undertaken
specifically to compare these alloys in representative sulphate melts under controlled
 Corrosion of austenitic steels in molten sulphate deposits 385

conditions. In this work emphasis has been placed on the role of the minor refractory
element alloy additions in influencing the deposit chemistry and thereby affecting
metal-oxide stability.
EXPERIMENTAL METHOD
1. Alloys and materials
Analyses of the alloys investigated are given in Table I. Specimens were in the form of 12ram
discs, 3ram thick, polished down to 600 grade emery and degreased in acetone.

TABLE 1. CHEMICAL COMPOSITION (wt. %) oF EXPERIMENTAL ALLOYS

Alloy C Si Mn S P Ni Cr Mo V Nb B

AISI 316 0.04 0.39 1.50 0,024 0.02 11.56 16.92 2.58 -- -- --
AISI 347 0.06 0.58 1.68 0.018 0.019 12.95 17.60 0.18 -- 0.74 --
Esshete
1250 0.08 0.56 6.4 0,009 0.027 9.50 15.60 1.03 0.23 0.93 0.004

Sulphate melts were prepared from analytical grade reagents and were dehydrated before weighing,
and again after mixing before each experiment.

2. Simultaneous thermal analysis (STA)

STA experiments were carried out in a decimilligram thermobalance* fitted with a Differential

Gas inlet

/Platlnlsed asbestoscatalyst
/

Specimen
crucible- / ~ 1 ~[~ Movable
furnace
y/
j/
crucible -

I ,/
/

If'
Gas outlet,q-- !
I
Heater
tapes

Nzbafflegas~'~"...... ~'~ il[]l Jl Balanceboxhd

~ Thermocoupleleads

I. ,~ Balance arm

FIG. 1. Experimental apparatus for simultaneous thermal analysis (STA).

*Stanton-Redcroft TR-01.
386 A. HENDRYand D. J. LEES

Thermal Analysis (DTA) head assembly (Fig. 1). The difference signal from the specimen and refer-
ence thermocouple in a crucible containing calcined alumina is amplifiedf and recorded together
with furnace temperature on a two-pen chart recorder.:l: Heating and cooling rates are controlled by
a linear variable programmer§ having a range of 0.5-10°C min -1.
The gas mixture used was N~ + 15 v/o CO2 ÷ 1 v/o 02 + 0.3 v/o SOs, passed over a platinised
asbestos catalyst immediately above the specimen head. The outlet end of the system was preheated
by heater tapes to avoid SO3 condensation (B.pt 44.8°C) which would disturb the gas equilibrium
and also affect the thermobalance record if deposition occurred on the specimen support rod. SOs
was removed from the outlet gas by bubbling through water traps.
In a typical experiment the system was set up with the weighed sample in position and flushed
with gas for lh. The temperature was raised at a pre-set rate over the range of interest and the weight
change, specimen temperature and differential temperature (AT) were recorded. All AT peaks
observed were determined both on heating and cooling and at different rates of change of temperature.
A complete cooling curve was determined at the end of each run. Platinum crucibles were used in
all of the experiments reported; a series of runs in mild steel crucibles was attempted, but in each
case the thermocouples failed owing to interaction with the crucible metal and oxide at temperature.
All of the melts and compounds examined were prepared from analytical grade reagents and
were either dehydrated in air before weighing or left in the hydrated state in order to use weight loss
and the ATpeak as an internal calibration.

3. Corrosionexperiments
The experimental apparatus is shown in Fig. 2, comprising a Stanton-Redcroft decimilligram
thermobalance with a modified specimen support rod holding a vitreous sihca crucible which con-
tains the specimen and sulphate mixture, the weight of which was approximately 6.5g in all experi-
ments. The alloy sample was placed in a layer of sulphate powder in the bottom of the crucible and
covered by the remainder.
The thermobalance and crucible were set up and flushed with the experimental gas mixture of
N~ + 15 v/o CO, + 0.3 v/o SO2 + 1 v/o O~ for lh with the furnace at 600°C in the raised position.
The gas mixture was not catalysed to produce SO8 by the reaction:

SO.. 5 ½0~ ~ SO3 (1)

as autocatalysis was observed to occur at the melt surface. The outlet was preheated and SOs was
removed from the gas stream as previously described. Tests were commenced by lowering the furnace
onto the specimen assembly and ended after the appropriate time by raising the furnace and allowing
the crucible to cool in the flowing gas stream.
Specimens were easily removed from the crucible as the molten sulphate did not wet the silica
during the course of the experiment. The alloy and solidified melt were then sectioned vertically and
one half was mounted in evacuated Araldite resin for metallographic examination by optical micro-
scopy and scanning electron microscopy (SEM). The other half was retained for X-ray analysis.
Energy dispersive X-ray analysis in the SEM was used to determine the quantity and distribution of
elements in the oxide scale. This was carried out by measuring the relative intensities of the Ka
emission peaks for the elements in question except for molybdenum, where, owing to the weakness
of MoKa emission at 17.3 kV, the MoL~ emission peak was used instead. As MoL, overlaps SKit a
calibration was carried out to determine the relative ratios of MoKu : MoLa intensity at a series of
beam excitation potentials using a pure molybdenum standard in order to separate the contribution
from MoLa and SKtt in scales containing both elements. The molybdenum concentration distribution
was determined by point counts at fixed distance intervals across the specimen.

EXPERIMENTAL RESULTS

STA investigation of sulphate mixtures

Decomposition or ferric sulphate. T h e e q u i l i b r i u m :

Fe203 + 3SO3 ~ - Fe2(SO4),~ f2)

fStanton-Redcroft DC amplifier STA661.
~Honeywell Electronik 194.
§Stanton-Redcroft LVP 10.
 Corrosion of austenitic steels in molten sulphate deposits 387

couple

Gos inlet

/
/"
/ / Movable
furnoce

Gas outlet

?opes

Nz baffle g a s ~ _

Balance box lid

Balance arm

Flo. 2. Experimental apparatus for thermogravimetric analysis (TGA).

has been discussed by Halstead and Laxton la in their investigation of the sulphation
of =-FesOs and ?-Fe=Os. The equilibrium SOs partial pressure (Pso,) given by these
workers was:

0.95 (4- 0.11) × 104

logpso, = 14.18 (4- 1.39) -- T (3)

where Pso, is in Nm -s and T is in K. The value of log Pso, as a function of tempera-

ture is shown in Fig. 3 with the equivalent curve for the reaction:

SO= + ½0= ~- SO3 (1)

calculated from data in the JANAF Tables" for a gas containing 0.3% SO2 and
1% O2. The decomposition temperature for ferric sulphate at unit activity in this gas
mixture, predicted from Fig. 3, is 560°C.
The present results for analytical grade ferric sulphate in a gas mixture of com-
position: N 2 + 15 v/o CO 2 + 0.3 v/o SO2 + 1 v/o 02 gave a decomposition tem-
perature of 573°C measured from the DTA curve and 555°C from the weight change
curve. These results are in reasonable agreement both with the calculated temperatures
388 A. HENDRY and D. J. LEEs

-I.0

q~
-2O
o~

-30

-40

-5.0
1.0 1.50

+x,O ~, K'~
FIG. 3. Log Psos as a function of 1/T for the equilibria:
Fe=Os + 3SO= ~ Fe=(SO4)s
SO= + ½0~--SOs.

and the value of 565°C from a gravimetric determination by Garrett and Penfold 15
for ferric sulphate in a gas mixture of N2 + 16% CO2 + 0.2% SO2 + 2% O2 which
gives approximately the same Pso, as the conditions of the present experiments.

Alkali iron trisulphates

An equilibrium phase diagram for the system Na2SO4-K2SO4-Fe2(SO4)a has been
constructed from available published information on the following binary sulphate
systems: Na2SO~-K2SO416 (Fig. 4); K~SO4-Fe2(SO4)su (Fig. 5); Na2SO4-Fe2 (SO4)s17
(Fig. 6); KaFe(SO4)a-NaaFe(SO4)a 2 (Fig. 7).* In Fig. 8 a section of the ternary
diagram at the alkali metal rich end is shown.
By inspection of these diagrams it is reasonable to assume that a low melting
point trough will exist within the ternary system extending between the alkali metal-
ferric sulphate binary eutectics, and with its minimum value lying on the conodes
through the minimum in the Na2SO4-K2SO4 liquidus curve, i.e. at Na2SO4 +
20 tool% K=SO4.
To test this supposition a series of compositions along section aa'-bb' in Fig. 8
were selected with nominal additions of 5 w/o, 15 w/o, 25 w/o and 50 w/o Fe2(SO4)8.
Melting points were obtained by STA. The results are presented in Table 2 and
*These phase diagrams arc summarized in Phase Diagrams for Ceramists, Levin et al. Vols. I
and II. American Cer. Soc. (1964 and 1969).
 Corrosion of austenitic steels in molten sulphate deposits 389

1 0 7 l ~
IO00
~384
8oc 825
,o
6oo'

4O',)

200
I
KzS°4
50
roD, %
N%S0 4

FIG. 4. The system K,SO4-Na~SO4 (Perrier and Bellanca~e).

plotted in Fig. 9 as portion a a ' - b b ' of the ternary system of Fig. 8. The STA curves
were used to calculate the actual mixed sulphate compositions by recording the weight
losses corresponding to the dehydration peaks at ca. 100°C. Only Fe~(SO4)a.9H20
was present in the fully hydrated state. These true compositions are used in Fig. 9.

TABLE 2. MELTINGPOINTSDETEgMI~D BY STA FOg ~gNAgV SULPHATE

MIXTURESBASEDONNa2SO4 + 20 moi 70 KzSO4
Nominal composition Melting Phases identified
w/o Fe~(SO~)3 point by X-ray diffraction
5.0 806 KNaSO4 + Na2SO4 + [F~Os]
15.0 550 KNaSO4 + (Na, K)3Fe(SO4)a +
hydrated salts + [Fe2Oa]
25.0 546 KNaSO4 + (Na, K)3Fe(SO4h 4-
hydrated salts + [F~O~]
50.0 540 (Na, KhFe(SO4)a -k hydrated
salts + [FenDs]

[ ] denotes trace amount.

The results indicate a minimum melting temperature of 530°C at approximately

30 w/o Fe~(SO4)3 (14 mol % Fe~ (SO4)a)and also that all compositions from 6 mol %
to 30 mol % Fe2(SO4)a are molten below 550°C. There exists, therefore, a wide range
of alkali iron compounds which will be present as molten deposits at superheater
operating temperatures.
X-ray analysis of the residues following melting point determinations confirmed
the presence of a solid solution series between KaFe(SO4)a and NaaFe(SO4)a (Table 2).
All of the compositions investigated contained trace amounts of haematite indicating
that some decomposition of ferric sulphate had taken place. Otherwise the 5 w/o
Fe2(SO4)a specimen had an identical diffraction pattern to that of the binary alkali
390 A. H~h'DRY a n d D. L. L ~ s

1071
lO00

80O /

L3 "~// 693
F,-" 60c 67

400 ,~
v ~C

200F
50
K2 SO4 Fe2(S04)3
tool %
FIG. 5. The system K=SO4-FeI(SO~)= (Rahm¢l and Jaegerlt).

900 - ,,,

700 " " ~

o
i--"500
300

I
I0
L
20
/ I
,50
L
40
,.,
No2SO4" tool % Fe2(S04)5
F[o. 6. The system Na=SO4-Fe~(SO.)= (Bol'shakov et al)7).

6oo~~. ~,~
5 0 0 ~ I
50
Nd3Fe 1804)3 tool % K~Fe (804)$

Fie. 7. The system Na=Fc(SO~)rK.F¢(SO~) (Cain and NelsonS).

metal sulphate mixture with the compounds KNaSO4 and Na2SO 4. With increasing
iron concentration the complex alkali iron trisulphate solid solution (Na, K)aFe(SO~)s
was formed in increasing proportion with KNaSO4 until, at 50 w/o Fe=(SO4)s, only
(Na, K)aFe(SO4)s was identified as the major component. The room temperature
X-ray photographs of all these specimens were complicated as a consequence of
 Corrosion of austenitic steels m molten sulphate deposits 391

./-~ J ] \1/\/I "~-

I T °C 1071

No Fe(S04)Z •

KFelSOd)~

Flo. 8. Composite drawing of the ternary system Na=SO4-K~SO4-Fe~(SO4)s.

their hygroscopic nature by the appearance of hydrated salts in addition to the

anhydrous decomposition residue.
A compound containing 15 w/o Fe2(SO4)3 (composition: 74 tool% Na2SO4 4-
20 mol % K=SO4 + 6 mol % Fe2(SO4)a) was selected as the sulphate melt for the subse-
quent corrosion experiments and a detailed STA analysis was carried out under a
covering gas of N2 4- 15 v/o CO~ -t- 1 v/o 02 4- 0.3 v/o SO2. The temperature range 20-
900°C was investigated with varying periods of isothermal equilibrium at selected tem-
peratures. A small weight loss and A T peak were observed at 100°C due to dehydra-
tion, and a second endothermic peak at constant weight occurred at 270°C, corres-
ponding to the low temperature transformation of compound (Na, K)aFe(SO4)s to a
random solid solution. The sample melted at 560°C, and was held at 600°C for 2 h

900

823

7o0

500 25 Na2S04

[5O~/o % ~o~csoA o "/o ]

FIo. 9. Experimentally determined melting points of ternary sulphate mixtures.

(Section aa'-bb' of Fig. 8).
392 A. HENDRYand D. J. L~Es

during which time a small weight loss occurred due to volatilization of alkali metal
sulphates. As the temperature was increased above 600°C a pronounced weight loss and
endothermic change in the A T curve was observed at 700°C (-4- 20°C) which continued
as the temperature rose to 900°C. At this point the rate of weight loss decreased
after a short time to a value approximately equal to the rate of volatilization of
Na2SO4 at 900°C calculated from the partial pressure data given by Halstead. 18
The total weight loss recorded between 700°C and 900°C was in accord with the
calculated value for decomposition of the weight of ferric sulphate in the melt accord-
ing to equation (2). This was confirmed by the cooling curve which had a solidification
peak, at 783-790°C, close to the value for the Na2SO4-K2SO4 binary. X-ray analysis
showed the residue to contain hydrated KNaSO4 with excess Na2SO4.
From this work it appears that the sulphate (Na, K)3Fe(SO4)3 is stable in the
prevailing gas potential and forms by sintering with eventual melting at 560°C. The
compound must form in the solid state below this temperature otherwise decomposi-
tion of uncombined pure, solid ferric sulphate would occur at ca. 560°C.
From the present results decomposition occurred at 700°C (4- 20°C) at which
temperature Pso, = 76.9 Pa. It is possible therefore, from equation (2), to calculate
the activity of ferric sulphate in the melt from:
p3
aF,, o,. so~ -- 1.5 × 10-12 (4)
aF,, (so4)~ = K(T)

where aFe~O3 = 1, and K(T) is the equilibrium constant at 973K.

The activity of ferric sulphate in the melt relative to the pure crystalline solid
(no data are available for heat of fusion of the melt) is therefore considerably lower
than an ideal solution model predicts.
Re-sulphation of Fe203 in alkali sulphate melts would be expected as temperature
decreases, and has been shown to occur, a5 This reaction is, however, kinetically less
favourable, being strongly dependent on access of SO8 to the iron oxide and, there-
fore, on the exposed area of the melt.
The results given above for the decomposition temperature of dissolved Fe2(SO4)a
also explain an apparent anomaly in previous investigations of these compounds. It
has been reported 1,15 that, as the temperature increases in the range 500-750°C, the
alkali iron trisulphate melts at 565°C and then resolidifies at ca. 700°C. A number of
explanations are put forward: for example, that 700°C represents the upper limit
of pyrosulphate stability, or that the complex trisulphate liquid goes into solid solution
in Na2SO4. The present work shows clearly that resolidification is a result of decom-
position of ferric sulphate at low activity in the melt by reaction (2) leaving a residue of
KNaSO4 + Na2SO4, containing Fe~O3 (Table 2). The melting point of this residue is
that of the alkali metal sulphate alone, 820°C.

Corrosion tests
The three alloys showed similar qualitative behaviour in the crucible corrosion
tests. Figure 10 shows thermobalance curves from these experiments, incorporating
scatter. The results show three separate stages of oxidation: (i) an initial rapid weight
gain, (ii) a decrease in rate of weight gain, eventually becoming zero, and (iii) a final,
 Corrosion of austeniticsteels in molten sulphate deposits 393

8O
~J
E
E AISI 316 ( Preoxidised )

o
vx
.¢_
g
g
(a

to

I I I ]
c) tOO 200 300 400
Time, h

F I G . 10. Weight gain curves for oxidation of steels in molten sulphate at 600°C.

approximately linear, weight loss. From STA analysis of the sulphate melt it is known
that the final weight loss section of Fig. 10 is due to volatilization of alkali metal
sulphate. Assuming the vapourizing species to be Na~SO4 (since the melt is 74 tool
Na2SO4 which has a higher vapour pressure than either of the other two constituents),
the value of the vapour pressure can be calculated from the final linear portion of the
curves in Fig. 10. A value of 2.40 ( i 0.7) × 10 z Pa was obtained for a flow rate of
300 ml min-~, which can be compared with the value given by Halstead~s for Na2SO4
at 600°C of 1.3 x 10-3 Pa. The agreement is good since the latter figure only applies
strictly in a static atmosphere, and a flowing atmosphere would be expected to increase
the apparent vapour pressure.
By extrapolation of the third stage weight loss back to zero time in Fig. 10 the
thermobalance data can be corrected for volatilization of sulphate to give the true
corrosion weight gain. This is shown in Fig. 11 where the results are normalized in
terms of weight gain per unit weight of sulphate melt. On this basis the resistance to
corrosion increases in the order: 316 < Esshete 1250 < 347. The third stage of the
curves shown in Fig. 10 now becomes approximately horizontal corresponding to a
very slow rate of weight gain. Corrosion takes place by transport of SO3 inward
through a liquid sulphate layer, but as the test proceeds and the melt becomes
saturated with Fe2(SO4)s then solidification occurs (see Fig. 9) and the rate of weight
gain decreases sharply.
Metallographic examination of the sectioned specimens showed consistent
morphological features common to all three alloys, but varying in extent. Figure 12
shows the SEM analysis of the scale layer on a corroded sample of AISI 316 steel after
400h at 600°C in molten sulphate. There is an inner layer rich in sulphur that also
contains molybdenum, surmounted by a multilayer scale of spinel that is rich in nickel
and chromium at its outer limits, which correspond to the original metal surface.
Outside this interface only iron oxide is found with trace quantities of nickel and
chromium. Esshete 1250 and AISI 347 have similar, but thinner, scale layers and the
manganese in Esshete 1250 is found to be associated with the sulphur adjacent to the
394 A. HENDRYand D. J. LEES

AISI .'516

T 0.15
?

c: 0.10
g

AISI 3 4 7

"~ 0.05
o
Z

I I J
0 I00 200 3()0 400
Time, h -t

Fro. 11. Normalized weight gain curves for oxidation of steels in molten sulphate
corrected for volatilization of alkali sulphates.

scale-metal interface. These observations are consistent with the accepted model of
oxidation of austenitic alloys which form a spinel-type oxide in which the inner layer
grows by inward diffusion of oxygen and sulphur anions and the outer layer forms
by slow outward diffusion of iron cations. The distribution of elements in the scale is
similar to the results of Salisbury and Birks 19 for high temperature oxidation of
Fe-Cr alloys in flowing SO~-argon mixtures although the present scales are much
thicker.

DISCUSSION
Dependence of corrosion rate on temperature
The STA results suggest a mechanism for the general dependence of fireside
corrosion rate on temperature in the operational range 500-750°C in terms of the
melting behaviour of alkali metal-iron sulphates as a function of SO8 partial pressure.
Consider a ferrous superheater tube in service interacting with the flue gas stream
via a deposit of ash and molten sulphate, through which a temperature gradient is
established due to the heat flux (Fig. 13).
The thickness of the molten sulphate layer is dictated by its thermal conductivity
and the temperature gradient. Thus, on the inner side of the sulphate layer, for a
given oxide thickness, the temperature is controlled by the steam-metal temperature;
on the outer surface the upper temperature is that at which ferric sulphate in solution
dissociates to Fe208 leaving a solid alkali metal sulphate residue. The pronounced
negative departure from ideality of ferric sulphate in solution will cause the decom-
position temperature to vary very little as a function of saturation solubility in the
sulphate melt. It is reasonable to accept the value of 720°C determined by STA,
therefore, as the upper temperature of the outer surface of the molten deposit. At a
greater distance from the tube surface a porous layer of iron oxide forms by de-
FIG. 12. SEM analysis of corrosion scale on AISI 316 (400h; 600°C; gas mixture N2 -]
15v/o CO2 + lv/o O2 ÷ 0.3v/o SO2).
(a) Electron image; (b) CrKa; (c) FeKa; (d) SKct.
 Corrosion of austenitic steels in molten sulphate deposits 397

e~" Fe~ F e ~~ SO~

I

Oxicle Sulphole m e l t Fe/0:~ Ash

c~

ts_

S~ flux)

Fro. 13. Schematic representation of transport processes in superheater tube deposits.

composition of ferric sulphate, the thickness of which is probably limited by physical

interaction with ash in the gas stream.
A gradient of SO3 partial pressure is established within the melt due to inward
diffusion from the gas phase. At the oxide-melt interface, the maximum Pso. is
governed by equation (2) in competition with the sulphidation steps:

SO~ ~ s e a + ½02 (5)

SO2 ~- ~$2 + 02 (6)

As the reaction products diffuse outward through the melt the effect of increasing
Psos and temperature are mutually opposed. By equation (2) increasing Psos pressure
at constant temperature increases the solubility of Fe~(SO4)3, whereas increasing
temperature at constant Pso. drives the reaction in the reverse direction.
The critical point in art atmosphere of composition N2 + 15v/° CO2 + 1 x O 2 +
0.3Y/. SO2 is 720°C. A continuous removal of metal is therefore effected in a tempera-
ture gradient leading to general corrosion of the tube surface at the point of minimum
ash deposition.
The observed 'bell-shaped' curves in service can be explained by the present model.
Figure 14 shows an example of the behaviour of superheater and reheater alloys.
Results were obtained by Rowley e t al. 4 using an air-cooled probe in a boiler burning
0.38 w/o CI coal at a gas temperature of 1050°C.
As the tube metal temperature increases the temperature difference across the
molten deposit, and hence its thickness, decreases until the point at which the tem-
pelature of the oxide--melt interface reaches 720°C. At this temperature the molten
layer becomes infinitely thin since no molten salt layer containing Fe2(SO4)8 can
exist above this temperature under the assumed gas conditions. The rate of corrosion
then decreases to a value equal to that of gaseous oxidation controlled by bulk solid
state diffusion processes through a solid layer. The important feature of this model
that the rate of corrosion in the temperature range in which the deposit is me lten
398 A. HENDRYand D. J. L~s

500

400

12%Cr steel
g ; \\\Fsshete
I \ ~,25o
300 J,-\ \',
/// \, ~ ,
/// /2 \'\ IAISI 316
// '\.
// \
x: 200 \.
\.
/ t
t \.\AISI 5 4 7
\
.~ I00 -
\
\
\
~5
I.)
\

o I I
6oo 650 700 750
Metal temperature, *C

FIG. 14. 'Bell-shaped' curves for superheater and reheater alloys in a coal-fired
boiler burning 0.38% C1 coal. Gas temperature 1050°C. After Rowley e t al. 4

is a function of the rate at which SO3 can be transported through the melt to the
oxide-melt interface. This assumes SOs to be the most rapidly diffusing gaseous
species in the melt and that the rate of chemical reaction at the inner oxide-melt
interface and diffusion of ferric ions away from the interface into the melt are suffi-
ciently rapid not to be rate controlling. Transport through the oxide layer is not taken
to be rate controlling as the oxide will reach a steady state thickness where the flux
of metal ions through it will equal that of SOa through the melt.
The diffusivity, D, of SO3 is given by Cutler and Grant ~° as 6 × 10-6 cmz s -1. A
diffusion flux of SOz can be calculated at any temperature from Fick's First Law:

J- -- D'APs°' (7)
x

where x is the thickness of the molten layer and A Pso, is the partial pressure gradient
through the melt, i.e.

A Pso8 = Psoa(melt/gas) -- Pso, (melt/oxide) (s)

Pso, (melt/gas) is the equilibrium value at 720°C for reaction (5)and Pso, (melt/oxide)
is the equilibrium value for reaction (2) with aF~(soa , equal to 10-12 relative to the
pure solid standard state (Fig. 3). In order to calculate Pso8 (melt/oxide) and x for a
range of metal temperatures a thickness of oxide of 50 Fm was assumed with a
 Corrosion of austenitic steels in molten sulphate deposits 399

thermal conductivity ( k o , ) o f 0.6W m-l°C-L *~ The temperature of the melt-oxide

interface is then calculated from:

Xoxid..(q/A)
T (melt/oxide) -- koX + T (metal) (9)

and the thickness of the molten sulphate from:

kso, ~-. (720 -- T (meU/oxia~))

x = (10)
(q/,4)

where (q/A) is the heat flux. A value of q/,4 = 0.47 M W m -2 was assumed. The
thermal conductivity of the sulphate, kso42-, is given by Turnbul122 as 0.4W m-l°C -1.
The thickness of the molten sulphate layer and Pso3 tend to zero as the oxide-
metal interface temperature approaches 720°C and the diffusion flux, J, therefore
becomes indeterminate. The values calculated for temperatures approaching 720°C
are shown in Fig. 15. The flux and rate of corrosion increase rapidly as metal
temperature approaches 680°C giving the upward half of a 'bell-shaped' curve, the
maximum value of which is in good agreement with the results of Rowley et al. 4
(Figure 14). The high temperature side of the curve will then drop sharply as the rate
of oxidation becomes controlled by gaseous diffusion in solid scales.

~6C

E
o. 7'(>(

,\
I
I \
!~0() 550 G(JO 650 }'00

Metal temperature, °C
FIG. 15. Calculated dependence of corrosion flux (SOD on metal temperature.

Influence o f alloy composition on corrosion rate

The variation in maximum corrosion weight gain between the austenitic steels
studied may be interpreted in terms of an acid fluxing mechanism related to the
refractory metal concentration in the alloys, as proposed by Johnson et al. ~s.24 and
Goebel et al.) 5 to account for the effect of molybdenum, tungsten and niobium on
the hot corrosion of superaUoys. Consider the following two cases:
400 A. HENDRYand D. J. LEES

Steel containing no refractory metal solutes. In the molten sulphate the rate of
corrosion of steel is increased relative to that of simple gaseous oxidation as a result
of the solubility of metal cations in the sulphate melt. Assume the metal cation to
be iron since it is present in greatest concentration in these steels and has been shown 15
to be sulphated more rapidly than the oxides of nickel or chromium. Corrosion occurs
as a result of dissolution of oxide in the molten sulphate at the scale-melt interface:

Fe,,Oa + 3SOs ~- Fe2(SO4)a (2)

and since Pso, increases from the scale-melt to the melt-gas interface, a driving
force exists for transport of the reaction products away from the reaction interface.
Sulphidation of the metal also occurs by reactions (5) and (6) releasing oxygen and
sulphur which diffuse into the scale. Sulphation of the oxide together with sulphidation
and oxidation of the underlying metal prevent formation of a coherent protective
layer.
As reaction proceeds the melt will eventually become saturated with metal sulphate
(equation 2) at which point no further dissolution of oxide can occur. It has been
shown, Fig. 9, that the melting points of Na2SO4-K2SO4 mixtures first decrease to
ca. 550°C with additions of Fe2(SOa)3 of ca. 10 tool % then continuously increase up
to, for example, 600°C at 30 mol % Fe~(SO4)a. Consequently, as the dissolution
of metal oxide in the corrosion test proceeds, the static sulphate mixture will become
solid, as was observed. Sulphidation and oxidation of the metal are inhibited since
there is no longer a molten layer to facilitate transport of sulphur and oxygen ions to
the metal surface and a protective scale develops leading to a decrease in the rate of
corrosion as seen in Fig. 10 (Stage II). The corrosion rate is then controlled by
diffusion of oxygen and sulphur through a protective scale giving a rate equal to that
obtained during simple gaseous oxidation (Fig. 10, Stage III). The weight gain due
to gaseous oxidation of these alloys at 600°C is negligibly small. The time required
to achieve saturation of the alkali sulphate melt by Fe~(SO4)a and consequent solidi-
fication has been shown to be a function of the volume of sulphate melt in the crucible
as predicted by this model.
A further test of the present model was devised in which the solubility of Fe2(SO4)3
in the sulphate melt in contact with a given alloy was altered by varying the equili-
brium SOs potential in the gas phase. From the equilibrium:

Fe2(SO4)3 ~ Fe2Oa ÷ 3SO~ + 3/2 02 (lO

the activity of Fe2(SO4)a is proportional to p(SO2)3 and to p(O2)a/2. Variation of

Pso, in the gas phase has the greater effect on this equilibrium, but it was experi-
mentally more convenient to vary Po,. Increasing the oxygen content of the N2+
15 v/o CO2+0.3 v/o SO2 carrier gas from 1 v/o O2 to 2 v/o 02 leads to an increase of
2.8 times in the activity of Fe2(SO4)3 by equation (11), and if its activity coefficient is
assumed to be constant the solubility increases by 2.8 times.
A specimen of Esshete 1250 was oxidized in molten sulphate under the standard
experimental conditions described above to the point of maximum weight gain and
the Po, was then increased to 2 × 103 Pa (2 v/o O2). The effect was rapid and the
 C o r r o s i o n o f austenitic steels in molten s u l p h a t e deposits 401

prevalent slight weight loss became a pronounced weight gain. Re-establishing 1 v/o 02
led to a decreased rate of weight gain which eventually became a weight loss over a
period of 24h.
This test confirms that the maximum weight gain corresponds to saturation of
the sulphate mixture with Fe2(SO4)8 in equilibrium with the gas potential. The slow
rate of re-establishment of equilibrium on decreasing the Po~ is due to separation of
Fe203 and SO3 from the melt which is supersaturated with respect to the gas potential.
The melt becomes a mixture of molten sulphate and solid iron oxide, and sulphation
of the metal continues until the sulphates become fully solid and a protective scale is
reformed on the metal.
The model also predicts that pre-oxidation should increase the rate of weight
gain due to a more rapid formation and saturation of Fe2(SO4)3 in the melt. If a
thick layer of pre-formed oxide exists it will be dissolved rapidly to reach a steady
state thickness where the flux of metal ions through the oxide balances the flux of
SO3 through the melt. This results in a more rapid initial weight gain than in the
absence of pre-formed oxide. Figure 10 shows a result with a 316 specimen after pre-
oxidation in air at 600°C for 7 days to produce a coherent low porosity duplex scale.
Note that the maximum weight gain (dependent on Fe2(SO4)a solubility in equilibrium
with the prevailing gas composition) is the same as for the polished specimens of 316
steel.

Steel containing refractory metal solutes. Consider iron to be the dissolving cation
and let the refractory metal solute be M(r) (molybdenum, vanadium, niobium or
tungsten). As in (i) the rate of corrosion is accelerated over that of simple gaseous
oxidation by dissolution of the oxide, enhancement of SO3 solubility, and sulphida-
tion and oxidation of the metal. In this case, however, corrosion is further increased
by the presence of the refractory metal solutes.
The solute M(r) is oxidized with the other major alloy elements:

M(r) + 3/2 02 ~ M(r)03 (12)

and reacts with oxygen ions from the sulphate melt acid/base equilibrium:

SOft- ~ SOs + 0 '~- (13)

thus:
M(r)O8 + 02- ~ Mfr)O, 2- (14)

Removal of oxygen in this way renders the sulphate melt more acidic and increases
the Psoa in the melt since:

aso4 2 -
Pso~ oc a o 2-
(15)

and the activity of sulphate ions, aso42-, is constant and approximately unity. The
solubility of Fe2(SO4)a is therefore increased according to equation (2), the time
402 A. HENDRYand D. L. LEES

required to saturate the melt is increased and a greater degree of oxidation and
sulphidation of the metal can occur before the melt solidifies and a protective scale
layer develops.
This model explains all of the experimental observations in Fig. 10. The initial
rate of corrosion is constant for the steels investigated since the mechanism of mass
transport is the same for all three and only the extent of attack per unit volume of
sulphate melt varies. The order of overall corrosion is in proportion to the increasing
concentration of refractocy metal solutes in the series AISI 347 < Esshete 1250 <
AIS1 316 (Table 1).
The effect of molybdenum on hot corrosion is generally held to be more pro-
nounced than that of niobium, vanadium or tungsten2a,~4 and this is supported by the
present results since AISI 316 and Esshete 1250 contain approximately the same
total refractory metal concentration but the former has a relatively high concentration
of molybdenum.
By multiple regression analysis of the maximum corrosion weight gain as a
function of alloy concentration (Table 1), an empirical relationship can be derived
for the effect of refractory metal solutes on corrosion, assuming the chromium and
nickel (or nickel + manganese) concentrations to be approximately equivalent. The
resulting expression is:

AWma x = 0.038 (w/o Mo) + 0.004 (w/o Nb + w/o V) + 0.066 (16)

where Aw is expressed in mg mm-Z.g sulphate-1. The effect of molybdenum is ten

times that of niobium and vanadium.
The constant term in equation 16 represents the weight gain which will occur on
corrosion of a 16-18 ~ C r + 9.5-13 ~Ni steel containing no refractory metal solutes
under the same conditions.

Correlation with boiler trials

Existing models of the fireside corrosion mechanism of superheater and reheater
alloys do not adequately account for the observed relative behaviour of different
materials under similar service conditions. It has been suggested that the superior
resistance of AISI 347 compared with AISI 316 is due to the difference in chromium
concentrations ranges within the AISI specifications, viz. 16-18~ for 316 against
17-19~ for 347, but this does not account for the resistance of Esshete 1250
(chromium range 14-16°/o)5 or the results of boiler trials with 12CrlMo tubes in a
final stage reheater which do not corrode at a greater rate than adjacent AISI 316.
It is proposed that the results of the present crucible tests, interpreted on the
basis of the acid fluxing mechanism, account for alloy service behaviour much more
satisfactorily than the chromium concentration argument. From the empirical
relationship of equation (16) the degree of influence of molybdenum, niobium and
vanadium on the corrosion rates of alloys in molten sulphates can be put in the
ratio Mo : Nb : V = 10 : 1 : 1. Thus, the equivalent concentration of total refractory
metal solute is:
Xm = w/o Mo + 0.1 (w/oNb + w/oV) (17)
for each alloy.
 Corrosion of austenitic steels in molten sulphate deposits 403

The results of the present crucible tests have been compared with data from probe
trials4 and in situ trials." These results were plotted as corrosion rate vs refractory
metal equivalent (equation 17), extrapolated back to Y~m = 0 and expressed relative
to the corrosion rate at E m = 0, in Fig. 16, which includes the present laboratory
results.
In view of the assumptions regarding the comparative effect of the different solute
elements the agreement is good for the range of temperatures involved. The corrosion
rate increases with increasing refractory metal concentration in harmony with the
acid fluxing model. Similar results have been reported for nickel alloys~ and for
nickel and cobalt alloys 23,54 It is noteworthy that two results for 12CrlMo from
probe trails4 appear correctly ranked. This is not unexpected mechanistically as in
the range 12-19~Cr corrosion is due to the sulphation of a magnetite-haematite
scale; the sesquioxide is unstable in the austenitic alloys owing to local chromium
depletion.
This work suggests that austenitic alloys of the type employed for superheater-
reheater applications can be ranked according to their refractory metal content for
the chromium, nickel (and manganese) range considered regardless of the detailed
composition of the molten fireside environment. Thus, if the corrosion rate of one
steel in a given boiler is known, the behaviour of any other similar grades of austenitic
steel could be inferred from equation (16) and Fig. 16.

2.5

2.0

e)
e

1050 gas/680 *C
+ metal
+ o 1050 °C gas/to60 ~Cmetal
:< Present work 600 *C
IOlO °C gas/650 *C
O.b + metal

~ 1 _ I _ _ , I
0 1.0 20 ,.5.0
E 1250 I~r • J
516
Refractory metal equivalent,

FiG. 16. Relative corrosion rates of superheater steels as a function of their refractory
metal concentration.

CONCLUSIONS
Simultaneous thermal analysis has confirmed the effect of ferric iron in depressing
404 A. HENDRYand D. J. LEES

the melting point o f alkali metal sulphate deposits typical o f those found on super-
heater tubes in coal-fired power generating boilers. Small amounts o f Fe2(SO4)a
have a significant effect and decrease the melting point o f the m i n i m u m liquidus
composition o f Na2SO4-K2SO4 mixtures from 820°C to 550°C. There is a range o f
composition in which the melting point o f N a - K - F e trisulphate is below the normal
range o f superheater/reheater operating temperature.
Under fixed Pso~ and temperature, the activity of Fe2(SO4)8 in the melt exhibits
a p r o n o u n c e d negative deviation from ideal behaviour. The decomposition tem-
perature o f dissolved Fe~(SO4)3 is therefore considerably higher than that o f the
pure solid c o m p o u n d and the resolidification behaviour observed in boiler deposits
in the temperature range 550-750°C can therefore be explained in terms o f decomposi-
tion o f Fe2(SO4)3 in the melt. This process has been demonstrated experimentally
and the mechanism o f corrosion o f alloys by molten sulphates and the observed
'bell-shaped' temperature dependence can be related to the melting point behaviour
o f the sulphates.
A model based on hot corrosion by an acid fluxing mechanism successfully
predicts the observed behaviour o f austenitic steels in service in boiler plant under
conditions o f molten sulphate attack.

Acknowledgements--The work described in this paper was performed in the laboratories of the
C.E.G.B. (Midlands Region) Scientific Services Department, and is published by permission of the
C.E.G.B. (Midlands Region).

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