Paper No.

CORROSION2004
04555
CAUSTIC STRESS C O R R O S I O N C R A C K I N G OF 304 SS
INCINERATOR MATERIAL

Ali Babakr and A.A. AI-Meshari

Saudi Basic Industries Corporation (SABIC)
SABIC Technology Center-Jubail, P.O. Box 11425, Al-Jubail, 31961
Saudi Arabia

Samuel Thomas M
Eastern Petrochemical Company (SHARQ)
Al-Jubail, 31961
Saudi Arabia

ABSTRACT

Under high temperature services such as in waste incinerating systems, failure can occur due to
obscure reasons that are not directly related to process parameters. Although, the chosen material for
the incinerator may be well suited, deposits in the system and some constituents of the process steam
may synergistically react to form aggressive species, which may initiate failure of the material. The
downcomer of an incinerator suffered sever cracking and loss of quenching water. Analysis,
interestingly, revealed that the observed caustic stress corrosion cracking (CSCC) was not directly
related to process parameters; rather, it was the results of the unexpected reactions of process
constituents. Thus, an understanding of the factors that may lead to such scenario may help in
extending the service life of the incinerator components. In this paper, a case study is presented to
provide an insight into the mitigation strategies to circumvent the failure of an incinerator down-
comer that had failed due to the presence of a caustic soda by-product that led to local stress
corrosion cracking.

Keywords: Incinerator, caustic corrosion, caustic stress corrosion cracking, intergranular,

transgranular, high temperature, sensitization, flue gas.

INTRODUCTION

Incineration systems are vital elements of the process used in petroleum and petrochemical
industries. Its chief purpose is to destroy contaminated product, out of specification product, and
waste products. Typically, an incinerator would operate at 1600-1800°F (870-982°C) or higher.
Copyright
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in any form, in part or in when
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be in writing NACE
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temperature applications and are widely used in the incinerator systems. Unfortunately, for austeniticare
Publications Division, 1440 South Creek Drive, Houston, Texas 77084-4906. The material presented and the views expressed in this paper
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stainless steels, sensitization is a great problem especially when operated at a range of temperatures
of 800-1600°F (425-870°C). This will make it susceptible to intergranular corrosion (IGC) and

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Government work published by NACE International with permission of the author(s). Requests for permission to publish this manuscript in any form, in part
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1
intergranular stress corrosion cracking (IGSCC). The susceptibility is believed to have risen from the
formation of Cr-rich carbides at the grain boundaries during thermal exposure to these
temperatures 1'2. Some authors have suggested that segregation of impurities such as P and S can
facilitate intergranular attack when Cr is not present, possible but of no valid proof. On the other
hand, from galvanic effect point of view, impurities can alter the local corrosion potential of the
boundary in relation to the adjacent grain. This is also true with grains near each other. Differing size
of grains, length of boundary, and heterogeneous precipitates can also be a contributing factor.

The scope of material selection would have to accommodate the high service temperature,
degradation (oxidation, carburization, sulfidation), and process parameters. In addition, the
mechanical properties of the material will also have to be clearly defined. This should include high
temperature corrosion resistance to the given environment, creep-rupture strength, and thermal
stability of the material in case of cyclic thermal load. In many reported cases, unscheduled shut
downs because of sudden failure were mainly due to high temperature corrosion and degradation.

Usually, it is not simple to understand or deduce the actual corrosive nature of the environment and
the possible corrosion reaction that might occur. Corrosive constituents might be obscure; although,
it is part of the process and no contaminants presence is possible. The most reported modes of attack
of corrosion are sulfidation and chloride in incinerators 3. Other forms of high temperature corrosion
can also manifest in combination, such as oxidation, salt-deposition, and nitridation, etc.

Rarely reported is the caustic presence or the possibility of formation at very high temperature that
lead to caustic stress corrosion cracking (CSCC). This paper reports the finding of an investigation
that was carried out to uncover CSCC in an incinerator environment.

BACKGROUND

At the incinerator down-comer quencher, the flue gas passes down the down-comer from the
incinerator to be cooled by water. Figure 1 shows a schematic of the incinerator and the quencher
along with the flow path of the flue gas and the quench water. The cooling water is brought from the
plant as wastewater (treated). The cooler will quench the gas from the neighborhood from 900°C to
90°C. The jacketed part of the quencher suffered multiple cracks and water was lost causing rise in
the flue gas exit temperature. In the past, there had been two failures of the same nature. No failure
analysis was done in the past. The composition of the flue gas is listed in table 1.

INVESTIGATION

Visual inspection of the samples showed severe damage (Figure 2). The inner surfaces of the
samples (flue gas side) were all unclean. Corrosion product color ranged from dark brown to
blackish and it was very resistant to mechanical removal. In addition, a thick deposit was present,
and mainly located at the lower part of the samples. Under the optical microscope it was mainly
black in color with some crystals, and some pores. The pores within were green in color.

Deposit did not cover the full exposed surface. It was present only in some parts. Deposit was
somewhat powdery and agglomerated. This enabled its analysis as topside and underside. Cracks
were many and visible on all samples. Sizes ranged from 0.5 mm to 120 mm and varied in directions.
The weld area had cracks on both sides. This was true for all samples.

The failure was located only in the upper portion of the incinerator down-comer, precisely where the
water is housed immediately next to the down-comer wall (jacketed part).

2
Figure 3 shows through thickness crack Figures 4 and 5 show the degree of sensitization and
corrosion damage. Photomicrographs show samples in either as polished condition or as etched.
They are representative samples of many showing high degree of sensitization and intergranular
corrosion. Figure 6 shows high precipitation of chromium carbides on the flue gas side. Figure 7
shows a thermally extended crack.

Material identification tests revealed the material composition is compatible with that of 18-8
stainless steel (304 SS). Samples of the deposit were analyzed by EDX and found to consist mainly
of sodium and oxygen. Deposit sample was viewed in two locations: bottom side facing the metal
and topside facing flue gas. Figures 8 and 9 show the characteristics of the deposit along with its
EDX analysis, respectively. Figure 10 shows SEM photomicrograph of clear sensitization and a
crack that is propagating in an intergranular way.

On the other hand, the surfaces of the material was plagued with mainly sodium and oxygen, could
be in the form of Na20. The XRD analysis of the deposit confirmed the presence of sodium
carbonate (NazCO3) as major, in addition to iron oxide (Fe203) as minor. The following table lists
these results.

A sample of the water used in the plant was analyzed using ion chromatograph (Dionex D-600). It
was found that C1- concentration was about 0.1 mg/L or 0.1 ppm. Sodium was about 22 ppm and
nitrogen was about 1.1 ppm. Neither sulfates nor sulfides were detected in the water. In addition, the
pH was 10.8 with a conductivity of 167 ~ts/cm and a total organic carbon of 590 mg/L.

DISCUSSION
Deposit & Corrosion Product
The build up started at the flue gas side. The deposit was only at the hottest part of the down-comer,
where the flue gas meets the quenching water. Once deposit is built, it presents local thermal
problem. The area where deposit builds up on the flue gas side at particular places and will cause an
increase in the down-comer wall temperature. A magnetic part on the samples was found, and it was
nothing more than Fe203 as a scale. The outer layer of the scale facing the flue gas will consist of
hematite (Fe203), then magnetite (Fe304), and at the metal oxide interface is wustite (FeO).
Oxidation in 18-8 304SS is at about 900°C (1650°F). Incidentally, magnetite is stable at about 693°C
to 1100°C (1279°F to 2503°F). It seems that oxidized regions had been oxidized to failure and was
the region were higher temperature developed because of deposit build up.

As can be seen in Figure 2, the reddish corrosion product was analyzed by EDX and found to contain
mainly iron (60%) and oxygen (30%) in addition to minor elements such as sodium (5%) and silica
(3%). At high temperature and with abundance of oxygen supply, it is suggested that in stainless
steels Fe203 will prevail, and minor Fe304 and no FeO products. This has been confirmed from the
XRD results as well. This is also the reason the regions nearby the some crack sites were magnetic
with no deposit build up. Other cracked sites had excessive build up of deposits mainly sodium
carbonate. This was apparent from the visible whitish color.

Several oxide types can form under such process conditions. Possible oxide(s) manifestation:
• Sodium (I) oxide (Na20): white in color, it is suspected that the sodium and oxygen detected
on the surface was of this type oxide. Especially, its melting point is 1135°C.
• Sodium (I) oxide (NaO2): yellowish in color and can form but will not remain since its
melting point is at 552°C and the service inlet temperature is at 900°C.

3
 Sodium (I) peroxide (Na202)" pale yellow in color, can form, but will not remain since its
melting point is at 675°C and the service inlet temperature is at 900°C.

• Iron (II) oxide (FeO)" black in color, its melting point is 1370°C.
• Iron (II, II) oxide (Fe304)" black in color, its melting point is 1600°C.
• Iron (III) oxide (Fe203): red-brown in color, its melting point is 1565°C.

• Chromium (VI) oxide (CrO3): dark-red in color, its melting point is 190-197°C, not possible.
• Chromium (IV) oxide (CrO2)" black in color, its melting point is 250°C, not possible.
• Chromium (III) oxide (Cr203)" green in color, its melting point is 2330-2450°C, possible.

Corrosion started under the deposit as a localized form (gouging). Later, intergranular corrosion was
established and it was easy for it to continue in intergranular manner in already sensitized material.
The presence of sodium hydroxide, as caustic, and the process temperature were the cracking factor.
As NazCO3 deposit accumulates, it will react with the quenching water to produce sodium hydroxide,
concentration of sodium hydroxide will increase with time. This process is continuous as more
NazCO3 is supplied through the flue gas and more water is introduced. The resultant reaction will not
be coveting the entire exposed surface; rather it will be occurring and coveting only selected points.
Sodium hydroxide at this stage of concentration (no means of truly knowing) and temperature of 600
to 900°C can be assumed hot caustic and will be enough to induce and propagate caustic SCC 4'5.

High Temperature Effects

The material was found sensitized because of high temperature exposure. Chromium carbide
precipitates at temperatures in the range of 427°C to 871°C (800°F to 1800°F), and are richl with
chromium. This makes the matrix near the grain boundaries depleted of chromium. Depletion of
chromium near grain boundaries makes it the weakest electrochemically and less resistant to
oxidizing and reducing acids. Hence, it becomes sensitive to the environment. This made it possible
for corrosion to attack the weakest point in the matrix, which is the grain boundary and leach out the
chromium carbides. This can be seen in the Figures. Sensitization is not detrimental in itself, unless
the metal is going to be in contact with an environment capable of generating corrosive species.

At an optimum stage of sodium hydroxide concentration, and under the influence of the slightest
amount of remaining residual or thermally induced stresses, the crack will propagate. Residual stress
is doubted, considering the length of time and the high operating temperature of the inlet. Crack
propagation of austenitic stainless steel in caustic solutions is faster than that observed in carbon and
low alloy steels 7. It has been reported 7'8 that less than 0.2% hydroxide in water may be capable to
induce cracking in austenitic stainless steels in few hours under concentrating conditions. In addition,
crack propagation may proceed at an astonishing rate of 6.25 mm (0.25) per hour 9. The shape of the
propagating caustic crack is normally branched intergranular. This has been witnessed elsewhere in
low concentration 10% of sodium hydroxide at 100°C and 316°C 6.

The concentration of OH- will continue and will drive the local pH to a very high point where the
protective oxide is no longer able to form, particularly in high operating temperature as in this
case 6'9'1°. Figure 11 shows the safe temperature limit in concentrated caustic for austenitic stainless
steel types 304, 347, 316 and 321. As long as the area remains alkaline, the mode of cracking is that
of caustic embrittlement and continues to occur in that way.

4
Flue Gas Constituents
It has been mentioned earlier, Table 1, that the flue gas contains oxygen 02, water in liquid and
vapor phase, carbon dioxide (CO2) (although CO presence is not doubted), nitrogen (N2) and sodium
carbonate (Na2CO3) deposits. Sulfur is absent and it was not detected.

Sodium carbonate is known to be very soluble in water and will decompose on the surface in the
presence of water according to following reaction:

NazCO3 + 2H20 ---->2NaOH + H2CO3

The decomposition will produce sodium hydroxide (caustic) and carbonic acid. This also explains
the presence of white deposits on some parts of the samples. This reaction is responsible for
producing the necessary NaOH for intergranular corrosion to occur in already sensitized steel

It seems that in this service, corrosion was initiated from flue side. At this elevated temperature,
(neighborhood of 900°C) the material is already suffering sensitization. Localized corrosion in the
form of gouges started due to deposit build up, which concentrated sodium hydroxide. Intergranular
corrosion later propagated from the bottom of gouges. This has been shown in the previous sections.

Changing the material to others that may be resistant to corrosion and mainly stresses such as those
with higher nickel (1'30%) content (Inconel 800, 690, and 600), or E-Brite or 7-Mo-SS 12, may be an
alternative, but high cost will be implicated. Austenitic stainless steels such as 304, 310 and 316
possess excellent corrosion resistance but are not immune to stress corrosion cracking. Although
within the known family of stainless steels there are those that can handle corrosive environment
more than 304 and 316, but their mechanical properties will be greatly compromised.

Hence, coating will be a necessary approach to extend the material service life. Changing metallurgy
to better austenitic stainless steel such as 31 OH would be even better.

CONCLUSION
The failure of the incinerator down-comer was the results of caustic embrittlement. It was found that
corrosion and cracking started from flue gas side. The more water was available, the more it reacted
with the deposit and produced sodium hydroxide (increasingly), and pH was driven towards higher
alkalinity; this prevented the protective film from developing. In addition to gouges, pits developed
and cracks proceeded in an intergranular and transgranular manner. All of the samples showed a
sensitized structure, and sodium was detected in all samples. Almost all pits, gouges, and cracks
were filled with oxides. Crack propagation to failure was assisted thermally. Ultimately,
understanding of possible interaction of the process constituents is essential.

REFRENCES

0 F. Schneider, P. Muraleedharan,, B. Schltiter, G. Barkleit, K. Mummert,

EUROCORRJ98, p. 129, Oct. 1998.
, D.W. Sandusky, S.J. Armijo, W.J. Wagner, J. Nuclear Mat., Apr. 1973, 46, (3), 225-243.
3. H. Ahluwalia and G. Lai, Corrosion/97, paper no 162.
4. I.L. Wilson, F.W. Pement, and R.G. Aspden, Corrosion/72, paper no. 61, NACE,
Houston, TX, 1972
° A.R. Mcllree and H.T. Micheles, Corrosion, 3,2, 1977
6. M.J. Estmacher, Corrosin/2001, paper no. 01496, NACE, Houston, TX, 2001
7. E. Howells, Corrosion Technology, Nov. 1960, p. 369.

5
 ° G.C. Wheel, POWER, Sept 1960, p.87.
9. D.A. Hansen, and R.B. Puyear, Materials selection for hydrocarbon and chemical plants,
Marcel Dekker, INC., 1996
10. J.K. Nelson, Corrosion, 13,1987, p. 1175.
11. T.A. Bold, J.W. Martin, and J.C. Tverberg, Duplex Stainless Steels, R.A. Lula, Ed.,
ASM, 1983, p. 169.
12. M.O. Speidel, ARPA Handbook on Stress Corrosion Cracking, R.W. Staehle and M.O.
Speidel, eds. 1976.

TABLE 1
COMPOSITION OF THE FLUE GAS

Constituent H20 02 N2 CO2 Na2CO3

Flow Rate
144 15.7 24.7 104
(Kg.mol/hr)
Partial Pressure 1023.7 49.8 111.6 175.6 739.3
mm-hg

TABLE 2
LIST OF XRD RESULTS

Compounds Nomenclature Phase ~Wt%

Na2CO2 Sodium Carbonate Major 55
Na2CO2.H20 Thermonatrite Major 31
NaFeO3 Sodium Iron Oxide Minor 10
Fe203 Iron Oxide (Hematite) Minor 4

6
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i
l
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INCINERATOR- H- 1801 "-,,.

~t Mating flange to
@
quencher

Flue gases at

o t 900 deg C Damaged

downcomer
parts- SS 304

,. @ . _ _---+q Water flowing down

QUENCHER- V-1802 ,~- -:-~ the corroded part
(Enlarged view) from jacket

~'1- Flue gas

~ I-4-_ _.z.~.

.~. ~,. __. _ __ __.__.

IN

Water seal

FIGURE 1 - Schematic of the incinerator and quencher, flow of the flue gas and quench water.

7
 (a)

~ili~, ', ]iiiiiiiiiii!~L~!!ii~!i'!~i!i;~iii!i~:~"~

2'
Nil;liliiiii i!ii!ii~i~i:]ii!ii!i!i~~Ni!~'~' ::

!~i:iiiii;iil,~::~ ....... ~:;r:.. ....... ~!iiiiii

ilil!ii~!iii!iiii~i .....
ii::ilii!~i!i!liiiililll~,.i. . '"
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:

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.:,:!iii:~i~i~;;~,i.;)i]iii!'[)i;!:i~i!iiiii

(b)

FIGURE 2 -Photos of samples in the as received condition showing badly buckled section of the
incinerator downcomer. (a) Side facing the flue gas, while (b) notice the crack and the whitish
deposit. It was found to be sodium carbonates.

8
 ~i "~2 ¸¸~..... '.......i~i!~!!~ii ~!' ~!~i~ii~!~!Q!~iii~!~i!i~ii'i~ii'!i'i!!"~!~i~ii~'i~
~!~ii'i~iii' ~! ¸¸~i~ii!i "?!i,~i:i! ~ !~ i ¸~! ~i

FIGURE 3 - Optical micrograph showing a through thickness crack, 10X

FIGURE 4 - Optical micrograph in the as polished condition showing: primary crack, sensitization,
and a secondary cracking as transgranular cracking 50X.

9
 i

FIGURE 5 - Optical micrograph in the as polished condition clear sensitization and intergranular
corrosion, 200X.

FIGURE 6 - Optical micrograph in the as polished condition showing a cross section showing
chromium carbides, this side was facing flue gas (500X) Oxalic acid etchant.

10
FIGURE 7 - Optical micrographs showing thermal crack, transgranular, X400.

11
 (a)

K C,r Fake

1.00 2.00 3.00 4.00 5.00 6..00 7.00

(b)

FIGURE 8 - SEM photomicrograph showing surface of the deposit, bottom facing metal wall (a),
and its EDX analysis which shows that it mainly consist of sodium (41%) and oxygen (46%).

12
 (a)

Na
J

i. O0 2. 00 3. 0 0 4.00 5.00 6~. O 0 7. 00

(b)
FIGURE 9 - SEM photomicrograph showing surface of the deposit, top facing flue gas (a) and its
EDX analysis which shows that it mainly consist of sodium (35%) and oxygen (48%), Cr (0.5) and
C1 (1.3%).

13
FIGURE 10 - SEM photomicrograph showing clear intergranular corrosion and sensitization.

uL
O

ol , , , , l '°

N=OH~ ~ b t t i o n , ~%
FIGURE 11 - Sodium hydroxide concentration and temperature effect on the SCC susceptibility of
austenitic stainless steels 4'13.

14