We as a constellation marine provides an extraordinary guidance and supervision on passivation Tank

cleaning of a chemical tanker which is very efficient and economical.

There are several operations we had carried out to maximize the performance of passivation on chemical
tanker. The new advanced technologies in tank cleaning have raised the standards in marine areas.

Passivation is one of the most important post-fabrication methods to enhance the inherent corrosion
resistance of the stainless alloy from which the workpiece was produced. It is not a scale removal
treatment, nor is it like a coat of paint.

The freshly machined or polished steel surface automatically acquires this oxide film from exposure to
oxygen in atmosphere.

Practically however, contaminants such as shop dirt or particles of iron from cutting tools may be
transferred to the surface of the stainless-steel parts during machining. If not removed, these foreign
particles can reduce effectiveness of the original protective film.

The below mentioned two-step procedure can provide the best possible corrosion resistance:
1. Basic cleaning but it’s an overlooked procedure.
2. An acid bath, or passivating treatment.
On chemical tanker generally, passivation is done after discharging of wet phosphoric acid of fertilizer
grade, hot caustic soda, Sulphuric acid and after discharging palm oil fatty acid, the prolonged washing
with from hot salt water.

Passivation carried out by Nitric acid in an expensive affair as far as possible we should carry out
passivation by Nitric acid only.

Citric acid passivation is a second-best option after nitric acid. The biggest disadvantage of Citric acid is
that it’s not an oxidizing agent. Nitric acid is FOSFA banned. Citric acid is eco friendly it efficiently removes
free iron from the surface of stainless steel. It can be used in lesser concentrations then nitric acid.

Initial passivation readings should be taken reach to conclusion that COT is active or passive. If COT is
found to be active then order the amount of nitric acid, recirculation material and fresh water is required.

Pls find below recommended procedure but not limited to passivation done by Nitric acid.
Passivation procedure for Cargo tank capacity of 1000-1500 Cum.
A) Take 2.0 m3 of water in one tank, prepare all connection for recirculation’s. You can use tank cleaning
machine cycle or calculate using hose flow through i.e fill up 200liter drum with hose & note the time
taken to fill up 200liters, you can use the same calculation to achieve above qty or can use fixed machine
cycle in prewash mode. Once FW is added in the tank, carry out leak test. FW to be heated to 40C or warm
water to be added.
B) Always Add Acid to water (Tank Cleaning Machine Single pitch 1.5deg) 440 liters, (Nitric acid 68%)
purity) ensure PPE LEVEL 3 with acid resistant face hood (full face coverage) is worn, you can use
Butterworth.
pocket or tank dome use acid resistant hose if using Wilden pumps. We are making the solution strength
about 15%. While planning for passivation start with small tank & then go on bigger tank with spiking of
35litres nitric with 160litres of FW.
Presuming 4 tanks 4P/4S/6P/6S Nitric Acid Passivation 4P first tank, then spiking 4S (35 liter nitric+160
FW) followed with 6P (35 liters nitric+160 liters FW),
6S (35 liters +160 FW).
C) Test the recirculation connection prior adding acid to water by running the pump & repair/change
gasket if found leaking by ensuring personnel are wearing PPE.
D) Start the cargo pump slowly, check for leak. If no leak increases the pump pressure to start
recirculation, remove all personnel away from the location & monitor for leakage from catwalk. In case of
any leakage, stop the pump, wash thoroughly with water prior reconnecting. Use 2 fix machine with 1.5
deg pitch & then undertake recirculation.
E) Towards last stage flush drop line, drains manifold, venting only by PV valve allow vapors to come out
from PV valve only.
F) Recirculation timing to commence only when temp has attained, recirculate using 1.5deg pitch only.
Heating coil are shut once temperature of Solution is attained. Undertake recirculation for 4 hrs Once
completed stop the pump close the connection of Octopus & transfer this solution into other set of tanks
using fixed piping only. While transferring liquid ensure the solution fills the lines completely which can be
achieved by keeping Drop valve of another tank closed.
When Solution is received on second tank. Carry out the same procedure by adding another 35 liters and
165 liters of FW in next pair of tanks
N) After connection to be prepared for FW rinsing for 40min or more, check FW rinsing until ph=7,
after 10 min of FW rinse (Cold) only start flushing lines pumps, drain. Always start pump after 10 min since
it allows dilution below 10%.
O) Ventilation by Fixed gas free fan to commence on first tank, venting by PV valve, purge pipe or By pass
of Vacuum valve.

Usually it takes time to shift hose from one tank to other due to mist of nitric vapors hence include time
gap of about 1hrs which occurs normally due arrangement/shifting. During FW rinse tank cleaning
machine to be in Prewash mode.

Personnel safety is very important & hence suggesting advising crew and carry out Tool box meeting,
discussing hazards of nitric hazards exposure.
There should be ventilation for 2 days more the days of ventilation more will be passive layer build up
after 1 day of ventilation use the hot air in the blower this will help.

Passivation reading is recommended to be carried out by stenchecker -II, passivation reading meter in
Volts. Please follow the instructions as per manual and take average readings of all bulkheads and
passivation reports should be prepared and sent to office for review.

By

Capt. Manish Kumar – Master mariner Principal Consultant (chemical and oil/products cargoes)
Constellation marine services.

(Prime area of work – UAE ports, Fujairah, Abu dhabi, Ras Al Khaima, Mina Sagar, Sharjah, Ajman, Dubai,
Hamriyah, Jabel Ali, Bahrain, Kuwait, Qatar (Mina Hamad) (mesaieed), Egypt (Alexandria) or fuel, Sohar,
Muscat, Salalah).

Q. I am having trouble convincing a customer (computer hardware manufacturer) that you

only passivate stainless steel and not normal carbon or alloy steels. How can I proceed to verify
this with them. Is there an exact specification I can go to. This is all about having some tools
clean enough for a computer clean room environment.

A. Your customer may be confusing "passivating" with "passive". Many times a steel part
needs to be activated for plating or finishing because it has become passive. Passivating for
stainless means to remove the iron from the surface and create a nickel and chrome- rich
surface layer that is not as subject to rust (only iron "rusts"). Let your customer know that a steel
part will always have a propensity to rust - even if it has become passive, because the iron is
always exposed to the atmosphere. Hope this helps.
A. Herb:
You cannot "passivate" carbon steel. Passivation is removing the free iron and other
exogenous materials from the surface so that a good passive layer can be formed. In
the case of carbon steel, this is not possible. After cleaning with a good cleaner, there
are a variety of coatings that can be used for carbon steel to provide a corrosion
resistant layer, but passivation is not the correct process.

A. Passivating carbon steel. If carbon steel could not be passivated then there would
be no boilers made of carbon steel. Boiler steel passivation occurs by the Schikorr
reaction at about 300 °C or 30 bar pressure. A protective "passivating" magnetite layer,
a few microns thick forms by a reaction between clean, pickled steel and water. The
reaction lowers the pH of the boiler water. In practice, newly pickled boilers are
subjected to controlled passivation using very small quantities of chemicals to control
pH and prevent re-dissolution of new magnetite. The thickness of this magnetite layer
will continue to grow at a decreasing rate until it hinders heat transfer. The boiler is then
again chemically cleaned.

The chemical cleaning itself, by pickling, strips oxide layers from the boiler surface,
leaving the steel active and prone to immediate oxidation (rusting).

To stop this "flash-rust" disturbing the Schikorr reaction, the pickled boiler receives an
initial "temporary passivation". This involves dissolution of the flash rust in citric acid,
followed by raising the pH to the range 8.8-9.5 using ammonia, which keeps
sequestered iron in solution. Once the pH is correct, an oxidizing agent, for example
sodium nitrite is introduced. This reacts with the iron in the steel to produce a very thin
(40-100 Angstrom) layer of Fe2O3, which, when formed under these circumstances,
inhibits flow of ions through it, thereby passivating the steel. This passivity is easily
destroyed and is therefore temporary in nature (unlike passive oxides formed on
stainless steel).

For carbon steel items to be used for everyday use, coatings are indeed usually applied.
Some coatings involve chemical reactions in which iron from the steel plays a part (such
as zinc phosphating), while other, usually more durable coatings physically attach
themselves to the steel, for example paint. It is common that physically adherent
coatings are applied to steel that has been temporarily passivated by, for example the
formation of iron phosphate. Such phosphates are formed by dipping pickled steel into
hot dilute phosphoric acid solutions followed by exposing them to air to complete the
process. An example of such a process is phosphating and painting of car body parts.

For tools to be used in clean-room environments preference should be given to quality

stainless steel implements.
A. I think Trevor has confused conversion coatings with passivation. To begin with,
carbon steel boilers don't rust because the pH of the water is kept above the oxidizing
point of steel which is about 8.2 - 8.3. The magnetite coating is a chemically induced
conversion coating (also called black oxide), that if left in a pH environment below 8.2
will start to rust. If proper boiler chemistries and and periodic blowdown schedules are
followed, there should be no buildup requiring chemical stripping of the boiler tubes. I
have seen boilers that have been online for 10 years and more without needing a
chemical strip.

Parts that receive a phosphate treatment likewise are not immune to rust and cannot be
considered passivated. This is another example of a conversion coating.

To close, passivation is accepted as being a theoretically permanent condition. Passive means

to not be active enough for the next finishing step.

Q. Dear Trevor Tipton and Dan Brewer:

I liked your responses and would like to ask what is a good reference to read about the
passivation of Boiler interiors?

and is it possible to obtain magnetite based solely on NaOH/Na3PO4 and ammonia dosing for
surfaces below and above 180 °C and pressures above 100 bar?

best regards

A. Passivation is subjected to lot of conditions. Say when you talk about a boiler, carbon steel
tubes in generating section will have a reduced oxide in a state of magnetite. it remains intact
only when you treat the water and chemically condition the same. demineralised water, free
from oxygen and chloride,pH elevated to 9.0 to 9.5, free from free caustic etc. it is non
impervious to ionic intrusion.
Whereas if it is gamma ferric oxide, it will remain intact and it's P.B ratio is above 1.0 it is
impervious due to structural integrity and natural oxide growth rate during regular operation is
retarded and beneficial in all respects.

Q. I have heard a lot about stainless steel passivation using various chemicals. But is it
possible to passivate carbon steel piping using sodium hydroxide, hydrochloric acid, soda ash,
Rodine-213 (corrosion inhibitor) and glassy sodium meta phosphate.
Can you suggest alternative for the same.

A. Passivation is a state wherein we protect it from re-oxidation.

A chemically active surface is more prone to attack due to its active state after immediate
chemical cleaning. It is important to make the metal passive to prevent the re-oxidation and
there by preventing further corrosion
normally the medium is switched to an alkaline state after an acidic reaction with an oxidising
agent to get the passivation layer on to the surface.

A. Carbon Steel can be passivated using .25% NaH2PO4, .25% Na2PO4 and .5% NaNO2 @
150 degrees. Makes a passive phosphate layer.

A. Hi, Bart. Thanks, but yes and no. The primary issue here is in the semantics; the
word 'passivate' is just slang, not a specification, and slang can have a very broad
meaning depending on who is doing the slinging, such that nearly anything can be
'passivated': zinc and electroless nickel surfaces are said to be 'passivated' with
chromate conversion chemistry; steel surfaces are said to be 'passivated' with
phosphatization; and the phosphatization in turn is said to be 'passivated' with a final
chrome or chrome-free rinse.

But there is also a narrower meaning of passivation, referring to processes that react
with the chromium content of stainless steel and can therefore only apply to chromium-
bearing stainless steels, not carbon steels.

This narrower interpretation does have some validity: note that when you consult a chart
of the galvanic series, you find that active stainless steel is very different from
passivated stainless steel, whereas you will see no similar distinctions for "active" vs.
"passive" plain steel. Note also that there are recognized "standards" for "Passivation of
Stainless Steel" (e.g., ASTM A380 [link is to the practice at TechStreet] , ASTM A967 [link by
ed. to spec at TechStreet] , ASTM B912 [link by ed. to spec at TechStreet], AMS2700 [link by ed. to
spec at TechStreet]), but no such standards exist for 'passivation' of carbon steel.

As a warning to readers, do not attempt a nitric acid "passivation" of plain steel; it can
evolve toxic quantities of NOx.

Regards,

Q. Is it possible to passivate BI pipes? If it's possible, what is the recommended acid for
passivation? Is phosphoric acid applicable? Thank you.

A. Hi Liz. It is certainly possible to treat rusty steel with phosphoric acid to convert the fluffy
red rust to the more stable black rust. Whether this should be called 'passivation' is a semantics
argument over the use of that word rather than a technical issue. Some people consider the
word 'passivation' to have a very specific meaning that applies only to the processes used to
remove plain steel contamination from stainless steel.
A. M.,
Passive is actually a chemist's term, it is the opposite of active. Active refers to atoms or
molecules that "want" to react with something. Taking metals as a pertinent example, metal as
we think of it has an electron valence of zero, which is to say the number of electrons in orbit is
equal to the number of protons in the nucleus. However most atoms, including metals, "prefer"
to have a different number of electrons, in the case of metals they want to give some away and
become a positive ion in solution or become bonded to the atom that it gave its electrons to.
Surface oxidation is the most common route to this, for instance if you cut a block of aluminum
in half you can see the slight color change across the fresh surface as oxygen gas swoops in
and quickly forms a layer of aluminum oxide. The new oxide layer is "passive" because it is
happy and no longer want to react to anything, and as a bonus it seals off the zero valence
aluminum underneath from being able to react with anything.

This is all fine and good for the majority of nonferrous metals, but when iron forms iron oxide it is
not a nice and pretty layer, it turns to rust and falls off, exposing new iron to new oxidation.
Common methods to combat this are coatings of another material, such as paint, powder coat,
zinc (galvanizing), a chromate conversion coating, etc. There are also stainless steels, which
use chromium to form a chromium oxide layer over the iron, protecting it the same way the
aluminum oxide prevents further reaction in the underlying aluminum metal.

Anything that renders your surface less likely to chemically react with materials in the
environment can legitimately be called "passivating".

Stress Corrosion Cracking of Steel in Liquefied Ammonia Service - A

Recapitulation

A.W. Loginow
Self-employed consulting corrosion engineer retired from U.S. Steel Corporation

January 1989

Category: Incidents

Summary: The following article is a part of National Board Classic Series and it was published in the
National Board BULLETIN. (9 printed pages)
Introduction
The following article is a follow-up to "Industry Study Indicates Stress Corrosion Cracking in Anhydrous
Ammonia Storage Vessels," which appeared in the October 1988 BULLETIN. This recapitulation of
experiences with stress-corrosion cracking of steel in liquefied ammonia summarizes the subject over the
last three decades. From the many reports reviewed, an effort was made to concentrate on those that
would lead to a better understanding of the problem facing the industry today and suggest a solution to
the problem. The review is aimed toward a summary of the conclusions from various sources; specific
details are available in the referenced reports.

Abstract
Stress-corrosion cracking of steel in liquefied ammonia is traced from its early recognition in the 1950s,
from experiences in agricultural and industrial use from NACE (National Association of Corrosion
Engineers) recommended DOT (Department of Transportation) regulations to prevent damage, and from
laboratory studies to explain the factors involved. Control measures are discussed; including control of air
contamination, inhibition by water addition, postweld heat treatments, influence of the strength of the
steels used and the applied stress, and periodic inspection techniques.

Agricultural Ammonia
Soon after World War II the Mississippi State College proposed a method of injecting liquefied ammonia
directly into the soil as a chief source of nitrogen fertilization (ammonia contains about 82 percent
nitrogen). Because excellent results were achieved, very soon a large network of ammonia distribution
and application facilities developed, which used many pressure vessels constructed primarily of carbon
steels. Although liquefied ammonia had been used without significant difficulties for several decades in
the refrigeration, chemical and steel heat-treating industries, inexplicable ruptures of ammonia containers
in the agricultural service occurred soon after the introduction of ammonia into this service. A survey
indicated that about 3 percent of the pressure vessels failed within 3 years of service life [1]**. Thereupon
a research committee was formed by the Agricultural Ammonia Institute to determine the causes of
equipment failure and to recommend palliative measures. By evaluating the storage and handling
facilities and practices for liquefied ammonia and by conducting controlled tests, it was determined that
stress-corrosion cracking (SCC) was the most likely cause of the failures [2]. The probability of SCC
increased with increased stress level as well as with increased yield strength of the steel. Of the many
contaminants that could have been present in the ammonia, air was identified as the specific agent which
caused SCC. (Although at that time the normal carbon dioxide content of air was believed to be essential
to the cracking process, later studies modified that concept.) It was also shown repeatedly that at least
0.1 percent of water in the liquefied ammonia inhibits SCC of constructional steels used in the fabrication
of the pressure vessels for agricultural service. As the result of the studies the research committee
recommended [2] that:

1. Pressure vessels should be either fully stress relieved or fabricated with heads that are hot-
formed or stress relieved.

2. Extreme care should be used to eliminate air from the ammonia systems; new vessels must be
thoroughly purged to eliminate air contamination.

3. Ammonia should contain at least 0.2 percent water to inhibit SCC.

The report [2] also remarked that, inasmuch as each of these recommendations has limitations when
considered individually, all three should be followed to avoid SCC. The adoption of these
recommendations was very effective in practically eliminating SCC in carbon-steel vessels used in the
agricultural industry [3].
Industrial Ammonia
Outside the agricultural industry SCC began to occur in the mid-1960s, primarily involving DOT
Specification truck-transport cargo vessels. This onset of SCC may have been due to improvements in
ammonia production technology which resulted in a gradual increase of the ammonia purity, mostly by a
reduction of the water content which inhibits SCC [4]. An examination of 19 ammonia vessels, that was
performed at that time, included several steels representing a wide range of strength levels. Sectioning
eight of these vessels that had been in ammonia service for 8 to 23 years and conducting a detailed
inspection by a wet fluorescent magnetic particle technique of the entire interior surface did not reveal any
indication of cracks. However, two additional DOT Specification 3AA vessels contained stress-corrosion
cracks. The hardness of the steels, obtained in lieu of tensile strength, which did not contain SCC ranged
from 134 to 272 HV, and the hardness of the cracked vessels was 207 HV and 241 HV. The reason for
this lack of specificity with respect to the hardness (or strength) level is not known. Perhaps the applied
stress of the cracked vessels was high in relation to their strength, or the contamination of the ammonia
was at a detrimental level. The specific grade of ammonia that was contained in any of these vessels is
not known, but it can be assumed that it was metallurgical or refrigeration grade ammonia, which do not
contain appreciable amounts of inhibiting water (33 ppm max or 150 ppm max [5], respectively). SCC was
also found in three refrigeration system ammonia condensers fabricated of ASTM A515 Grade 70 steel
[6]. The condensers had not been postweld heat treated and the cracks were located in the base metal
near welds. Two refrigeration system ammonia storage vessels of this steel also showed SCC in cold
formed vessel heads near welds that were not postweld heat treated.

An ASTM A202 Grade B hot-rolled steel truck-transport vessel contained SCC in and adjacent to repair
welds [6]. Although the vessel had been postweld heat treated after fabrication, subsequent repair welds,
however, were not heat treated and the residual stresses caused stress corrosion to occur. Note that
Compressed Gas Association guidelines for the repair of truck-transport cargo vessels [7] permit "minor
repairs" without subsequent heat treatment; this aspect will be discussed in a later section. SCC in ASTM
A202 Grade B steel ammonia transport vessels that were heat treated after welding, however, was
conspicuous by being essentially absent.

In 1967 DOT reported about 8000 truck-transport cargo vessels in existence, a half of this number being
fabricated of quenched-and- tempered (Q & T) alloy steels (ASTM A517), which represented the upper
end of the strength range examined. At that time about 2000 vessels were examined by vessel
manufacturers for evidence of cracking, and about 400 vessels contained some defects, but the DOT
commented that most of the defects were associated with poor workmanship, the balance probably being
caused by SCC. In the period from 1965 to 1977 the writer examined eight cargo vessels that were
fabricated of ASTM A517 Q & T steels with a postweld heat treatment and that carried a variety of
ammonia grades, some of them without water inhibition [6]. The observed cracks, in all in-stances
identified by metallographic examination as being caused by SCC, occurred on the inside surface, mostly
in the lower quadrant of the vessel, that is exposed primarily to liquid ammonia at or within a few inches of
internal welds as well as in areas opposite external welds, especially opposite those welds that attach
load-bearing pads. Cracks were also associated with repair welds that were not heat treated after the
repairs.

Until the mid-1960s the service performance of high strength quenched-and-tempered steel (ASTM A517)
truck-transport cargo vessels was excellent [3]. However, as SCC started to occur in such vessels, NACE
recommended a set of preventive measures that were adopted in the U.S. as DOT regulations in 1968
and 1975 [8]. These regulations required that cargo vessels of Q & T steels in liquefied ammonia service
be used only for ammonia containing at least 0.2 percent water. (An initially permitted ammonia of at least
99.995 percent purity was later eliminated from the requirements, because this purity definition
considered only water and oil as impurities and did not include air as a contaminant). Cargo vessels of
other than Q & T steels were permitted for use with any grade of ammonia. The regulations also stated
that all new cargo vessels for ammonia service be postweld heat treated. A wet fluorescent magnetic
particle inspection [7] of the internal surfaces was also required of all vessels in conjunction with the
hydrostatic retest every 5 years. A major vessel fabricator reported that subsequent to these
requirements SCC damage to Q & T cargo vessels has decreased substantially.
Beneficial and Detrimental Factors
The experience of SCC with liquefied ammonia containers and the resulting regulatory activity in the U.S.
prompted several investigations to be conducted in laboratories to further determine the factors involved.
Radd and Oertle [9] suggested that the cracking was due to hydrogen embrittlement, that water additions
were acting to accelerate rather than inhibit cracking, and that the observed inhibition was due to
dissolved oxygen in water rather than intrinsically to the water. Based on accelerated tests with C0 2-
saturated ammonia, Naito et al. [10] proposed that SCC in the test environment was initiated by pitting
and propagated by hydrogen embrittlement. Addition of about 0.75 percent water to this environment
reduced the cracking. Also, the addition of 0.01 percent NH 4 C1 suppressed the SCC. Furukimi et al. [11]
proposed to cover up the SCC problem by decreasing the hardness of the surface of high-strength Q & T
steel to less than 190 HV by decarburizing the steel surface and controlling the cooling rate during the Q
& T treatment.

At U.S. Steel Research many investigations were conducted by the use of the slow strain-rate technique
[12]. This technique, which is effective in producing SCC in relatively short time periods, employed
dynamic straining to stress a specimen at a rate that is much slower than that used in a conventional
tension test. Wilde [13] developed special sampling and gas chromatography analysis techniques that
overcome the problem of selective evaporation frequently encountered in determining the small
concentrations of gaseous contaminants in liquefied ammonia. With respect to SCC by liquefied ammonia
most of the slow strain rate tests were conducted on the high-strength ASTM A517 steel. Deegan et al.
[14, 15] have demonstrated by the use of anodic and cathodic polarization, in conjunction with the slow
strain method, that SCC in air-contaminated ammonia is anodically controlled and that cathodic
polarization prevents cracking.

Hennecken [16] also found that SCC of carbon steel in liquid ammonia is anodic in nature, and expanded
further from polarization tests that oxidizers in ammonia increase the danger of SCC. The anodic nature
of SCC in ammonia was also verified by Wilde and Kim [17] who demonstrated by the slow strain-rate test
that aluminum, which is anodic to steel in air-contaminated ammonia [18], when coupled to the straining
steel specimen can prevent SCC, apparently by cathodic protection. However, the relatively high
electrical resistivity of liquefied ammonia and the resulting poor throwing power militate against a
successful use of cathodic protection by sacrificial aluminum anodes in combating SCC in industrial
applications. This reservation is supported by observations that SCC occurred in ammonia truck-transport
cargo vessels, which were equipped with aluminum baffles electrically coupled to the steel vessels [6].

The studies of the ASTM A517 steel also showed that uncontaminated metallurgical grade ammonia does
not cause SCC [14], but that an 0.38 psig over-pressure of air can result in SCC [15]. The latter authors
also showed that separate additions of either 9 ppm oxygen or 3 ppm nitrogen to the ammonia did not
cause SCC in A517 steel, but that SCC occurred when both of these contaminants were added together;
a smaller addition of 0.9 ppm oxygen together with 3 ppm nitrogen also resulted in SCC [15]. Later, Wilde
[13] showed that in the absence of nitrogen greater amounts of oxygen (200 ppm) can cause slight SCC
in plastically deformed steel. He also determined that 0.02 ppm oxygen (added as air to ammonia
containing 18 ppm water) did not cause SCC in A517 steel slow strain-rate specimens. As the air
contamination level was increased, marked SCC occurred between 1 and 200 ppm oxygen, and as the
air contamination was increased further the SCC severity became less pronounced until at an oxygen
concentration of 920 ppm and above SCC was not observed. The role of oxygen was also confirmed by
Lyle [19] who concluded from slow strain-rate tests that oxygen contamination is the primary cause of
ammonia SCC of steel, as well as by Farrow et al. [20] who concluded that oxygen contamination is
necessary for SCC of mild steel at a level of more than 5 ppm in commercial grade ammonia, but as little
as 1 ppm may be sufficient when water is absent.

The early conclusion by Loginow and Phelps [2] that a small addition of water inhibits SCC of steel in air-
contaminated ammonia was later confirmed in slow strain rate tests on A517 steel [14, 15, 21]. Deegan
and Wilde [14] also showed that for the degree of air contamination used (approximately 2 atmospheres
partial pressure of air at 25°C) a limit for the effectiveness of water as an inhibitor was observed at 0.08
percent, which is in very close agreement with the lowest amount of 0.1 percent reported earlier [2].
Hennecken [16] states that high oxygen contents in the ammonia require increased water contents to
provide inhibition against SCC in carbon steel, and conversely, that low oxygen contents could be
counteracted by low water contents. He also concludes from polarization measurements that the
presence of oxidizers in liquid ammonia impede the inhibiting properties of water. Examination of some
failures of agricultural and industrial ammonia vessels, that were discussed earlier, suggested that the
inhibition with water was not practiced continuously and thus resulted in SCC. In 1975, Poulson and Arup
[22] showed experimentally by the use of the slow strain-rate test on mild steel that when water-inhibited
ammonia is replaced with a water-free air contaminated ammonia, cracking started without significant
delay, thereby confirming the suspicion that an intermittent exposure to uninhibited ammonia can result in
cracking.

Although cracks in truck-transport cargo vessels and storage spheres appear mostly in the lower part that
is continuously exposed to liquid ammonia [2, 6, 16], various reports from Europe were concerned with
SCC in the vapor space of storage spheres (mostly fabricated of low-strength carbon steel without
postweld heat treatment of the entire sphere) that contained water-inhibited ammonia. These
observations suggested that the inhibitive properties of water in liquid ammonia are not transferred to the
vapor phase. Studies by Ludwigsen and Arup [23] showed that ammonia which condenses on a cool
steel surface at nonequilibrium conditions, such as on a cool night, is capable of causing SCC. They
concluded that such a condensed ammonia contains much less inhibiting water and much more
detrimental oxygen than the liquid ammonia from which it evaporated. Later, Brown confirmed by
calculation the paucity of water in the vapor over liquid ammonia [24], and Wilde confirmed the
enrichment of air in the vapor by experimentally determining the partition coefficients between liquid and
vapor phases of ammonia to be 587 for oxygen and 603 for nitrogen [13]. Ludwigsen and Arup [23]
suggest that the liquid ammonia be maintained at a temperature that is lower than that of the steel in
contact with the ammonia vapor to prevent condensation and consequent SCC. This approach apparently
does not avoid SCC in the meniscus between vapor and liquid. Lunde [25] reports that SCC occurred in
the vapor phase when the steel was at ambient temperature, whereas cracking was observed only in the
meniscus when the top of the container was warmer by 5°C than the water-inhibited liquid ammonia and
condensation did not occur.

The environmental effects, that are summarized above, together with electrochemical studies led to the
formulation of a mechanism of SCC Gf constructional steels in liquefied ammonia [15, 21].

"In oxygen contaminated ammonia an adsorbed film exists on the steel surface which maintains the
corrosion potential at very noble values. During straining after yield, breaks in the film expose film free
metal at slip steps, and this metal dissolves rapidly under the noble potential imposed by direct galvanic
coupling to the filmed metal surface.

In the absence of any other impurity, oxygen has the tendency to refilm the bare metal and to some
degree inhibits the severity of SCC depending on the concentration and the strain rate. Nitrogen
dissolved in the ammonia inhibits the filming of the bare slip steps by a process of 'competitive adsorption'
with the oxygen and consequently increases the severity of SCC through a process of adsorption rather
than through a process of electrochemical origin. Water inhibits SCC by acting as an additional film
former which hastens passivation and healing of film breaks at slip steps"[18].

In this proposed model no mention is made about the contribution of carbon dioxide to the SCC process.
Wilde [13] has shown that, contrary to the early conclusion that carbon dioxide is essential to the cracking
process [2], this normal constituent of air when added to ammonia resulted in severe general corrosion,
but not SCC; for SCC to occur, air must also be present. In this study Wilde [13] also examined the
effects of various other contaminants and concluded that CO, CO+O 2, CH4, SO2, S02+02, NH4C03,
(NH4)2CO3 NH4N03, NaN03, N0, N02, N20, NaC1, NH4C1, NaN02, and NaNH2+air did not cause SCC
when added to an air-free test ammonia. Some of the test additives (S02, S02+02, NH4N03, and NH4 C1)
caused general corrosion to varying degrees.
Although it has been shown convincingly that additions of water on the order of 0.1 percent and more can
effectively inhibit SCC in air contaminated ammonia, there are end uses of ammonia in which even such
small amounts of water cannot be tolerated, such as in metal heat treating or refrigeration applications.
Therefore, some studies were made with additives that would be compatible with the end use of
ammonia, primarily amine compounds [13]. The tests showed that some inorganic amines and
ethylenediamide inhibited cracking in air-contaminated ammonia. Because the molecular constitution of
hydrazine (N2H4) is similar to that of ammonia (NH3), this compound was subjected to further tests at
concentrations ranging from 0.002 to 1.0 percent. The inhibitive properties of hydrazine in air-
contaminated ammonia were observed at concentrations of 0.025 percent N 2;H4 and above. Apparently
hydrazine acts as an oxygen scavenger inasmuch as in a hydrazine-treated ammonia, that was initially
contaminated with air and which subsequent to the hydrazine addition did not cause SCC, the oxygen
content had decreased to zero. The inhibitory effects of hydrazine and water were also reported in
relation to mild steel as well as those of ammonium carbonate, ammonium bicarbonate, and carbamate
[20]. Lyle [19] reported that water, methane, and nitrogen exhibit inhibiting properties, the latter being at
variance with the findings discussed earlier [15, 21].

Preventive Measures
The preceding discussion of practical experience and the many investigative studies of SCC of steels in
liquefied ammonia service suggest several measures that could prevent SCC or reduce the probability of
cracking. However, it should be recognized that each measure has limitations when considered
separately. For maximum benefit as many procedures as possible should be employed in the attempt to
combat SCC.

1. Air contamination (even a few ppm) is considered the primary cause of SCC of steels in liquefied
ammonia. It is therefore good engineering practice to purge new vessels of air and to eliminate
any conceivable possibility of air ingress into the ammonia handling system, such as at
detachable ammonia transfer points. Because air tends to concentrate in the vapor space above
a liquid ammonia pool (there is about 600 times more air in the vapor phase than in the liquid in
equilibrium with it) it is advisable in the case of large storage spheres to continuously condense
the ammonia vapor with a simultaneous discharge of the noncondensables, which is mostly air,
and to return the condensed liquid to the vessel. For relatively small units it was demonstrated
that a bleeding or boil-off method can effectively remove air from ammonia to avoid SCC [2, 13].
Good results in reducing SCC damage to storage spheres have been achieved by a careful
control of the oxygen content in ammonia having a low water content [26].

2. Similar to the detrimental effect of oxygen, the inhibitory effect of water content in liquid ammonia
has been well documented, the optimum dose apparently being 0.2 percent water in those
applications where this amount of water can be tolerated although it was suggested that a lower
water concentration may be adequate when the oxygen content is low [16, 20]. Note that for
effective inhibition of SCC the required water content must constantly be present in ammonia.
Should the water content drop below the critical concentration even for a relatively short time, as
by influx of water-free ammonia into a vessel, the irreversible-SCC damage can occur. Thus it is
important to monitor the water content on a frequent and regular basis and to replenish the water
if it starts to fall below the critical concentration. In metal heat treating and refrigeration
applications where this low concentration of water in ammonia is undesirable, laboratory tests
have shown that 0.025 percent hydrazine addition is adequate in inhibiting SCC. Although
industrial utilization of hydrazine in ammonia is still forthcoming, such use of hydrazine should
verify the laboratory findings.

3. The inhibitory effect of water may not be realized in the vapor space of liquid ammonia storage
tanks, and calculations and laboratory studies indicate that measures, which prevent
 condensation of ammonia on the steel surface, would tend to avoid SCC. Simultaneous
reduction of the oxygen content of the ammonia vapor should also be beneficial.

4. Postweld heat treatments are effective in substantially reducing the probability of SCC of steel in
contact with air-contaminated ammonia. Although postweld heat treatments are frequently
considered only from the standpoint of reducing the residual stresses, it should be recognized
that such thermal treatments result in two consequences, both of which are beneficial in
reducing SCC. First, properly conceived and executed thermal treatments can substantially
lower the residual stresses that result from fabrication (welding and cold forming), erection, and
restraint of the steel structure, such as storage sphere. Secondly, an appropriate postweld heat
treatment can significantly reduce the peak hardness in the heat affected zone (HAZ) of the
weldment [16]. Thus, a hardness peak of 443 HV in the HAZ of an ammonia tank of ASTM A202
Grade B hot rolled steel was reduced to 280 HV by a postweld heat treatment, and similarly a
447 HV peak hardness was reduced to 290 HV in an ASTM A517 Q & T steel weldment [6].
Such reduction in HAZ hardness benefits the resistance to SCC, especially in conjunction with
other measures. In this context note also that guidelines promulgated by the Compressed Gas
Association for repairs of vessels permit minor welding repairs to be performed without a
subsequent heat treatment [7]. However, the size of the area repaired by welding or the extent of
welding do not affect the hardness of the HAZ and its susceptibility to SCC. Therefore from the
standpoint of avoiding SCC, it is good engineering practice, that steel equipment for liquefied
ammonia service be heat treated after any welding operation regardless of size, which is a
requirement in the United Kingdom [27]. Although it is generally considered to be difficult and
costly, a successful full-scale heat treatment of a large fabricated and erected storage sphere
was reported from Japan [28]. Shot peening has been proposed to reduce residual stresses in
areas of weld joints or even to induce compressive surface stresses. However, experience has
shown that this approach only reduced temporarily the incidence of ammonia SCC, but did not
prevent it [16, 27, 31].

5. It is recognized that, in general, the probability of SCC of steel in liquefied ammonia service is
the greater, the higher the strength of the steel. The formulation of a lower strength limit, below
which SCC would not occur, is not practical because it depends on the level and nature of
contamination, the degree and nature of inhibition, the magnitude of residual and operating
stresses and the operating temperature. Nevertheless, a lower-strength steel appears to provide
a higher degree of resistance to SCC than a higher-strength variety. With respect to the stress
that exists in a steel component other aspects pertain; the upper limit is governed by applicable
statutory regulations, and the lower end, which is desirable from the standpoint of combating
SCC, is governed by the operating pressure, the technologically achievable reduction of residual
fabricating stresses, and economic and safety considerations. It is good engineering practice to
avoid stress concentrating features. Note also that if SCC has initiated, the effective stress at the
tip of the crack can be very high indeed. Novel design aspects, such as external reinforcements
that would place the interior surface of a tank in compression, could reduce the operating stress
level and benefit in decreasing the likelihood of SCC.

6. Many catastrophic failures, with resultant personal injuries and property damage that have their
origin in SCC, could be avoided by periodic and frequent inspections of the steel surfaces that
are in contact with ammonia, and by making repairs when needed. Cracknell [26] has proposed
an inspection schedule for as-welded carbon steel vessels that is based on oxygen and water
contents. Guild [30] recommends inspections to be conducted both before and after pressure
testing of storage spheres, because fine cracks can open up during the pressure test and
 become visible afterward. In the writer's experience, the most sensitive inspection method for
detecting the frequently very fine stress-corrosion cracks is the wet fluorescent magnetic particle
method with an alternating current yoke 16, 7, 31]. An acoustic emission technique [32], which
detects actively propagating cracks by sensors applied to the outside of an operating vessel,
could furnish a continuous report on the soundness of the vessel if equipped with appropriate
monitoring, processing, and warning devices.

References**

1. T. T. Dawson, Welding Toumal, vol. 35, 1956, p.568.

2. A. W. Loginow and E. H. Phelps, Corrosion, vol. 18, No. 8, 1962, p. 299.
3. E. H. Phelps, Ammonia Plant Safety, vol. 16, 1974, p. 32.
4. D. R. Pratt, Battelle Pacific Northwest Laboratories, 1976.
5. R. B. Teel, ANL/OTEC-BCN-008, Report, March 1980.
6. A. W. Loginow, Materials Performance, vol.15, No. 6, 1976, p. 33.
7. CGA Technical Bulletin TB-2, 2nd Ed., Compressed Gas Association, New York 1975.
8. Federal Register, vol. 40, No. 113, June 11, 1975; and revisions. Federal Register, vol. 40,
No.190, September 30, 1975.
9. F. J. Radd and D. H. Oertle, NACE Annual Conference, Chicago, Illinois, 1971.
10. N. Naito, W. Hotta, and H. Okada, "Accelerated Test Method for SCC of High Strength Steels in
Liquid Ammonia Environments", Manuscript, 1973.
11. O. Furukimi et al., Lecture No. S1371, ISIJ Meeting, 1981.
12. C. D. Kim and B. E. Wilde, Stress Corrosion Cracking - The Slow Strain-Rate Technique, ASTM
STP 665, G. M. Ugiansky and J. H. Payer, Eds., 1979, p. 97.
13. B. E. Wilde, Corrosion, vol. 37, No. 3, 1981, p. 131.
14. D. C. Deegan and B. E. Wilde, Corrosion, vol. 29, No. 8, 1973, p. 310.
15. D. C. Deegan, B. E. Wilde, and R. W. Staehle, Corrosion, vol. 32, No. 4, 1976, p.139.
16. H. Hennecken, Dissertation, Technical University Munich, Germany, 1984.
17. B. E. Wilde and C. D. Kim, Corrosion, vol. 38, No. 3, 1982, p. 168.
18. D. A. Jones and B. E. Wilde, Corrosion, vol. 33, No.2, 1977, p.46.
19. F. F. Lyle, Final Report DOT-FH-BMC-11-8568, 1976.
20. K. Farrow, J. Hutchings, and G. Sanderson, Br. Corr. J. vol. 16, No 1,1981, p.11.
21. D. A. Jones, C. D. Kim, and B. E. Wilde, Corrosion, vol. 33, No. 2, 1977, p.50.
22. B. Poulson and H. Arup, Proceedings - 7th Scandinavian Corrosion Congress,1975, p. 661.
23. P. B. Ludwigsen and H. Arup, Corrosion, vol. 32, No. 11, 1976, p. 430.
24. R. S. Brown, AIChE Symposium, Safety in Ammonia Plants, 1982.
25. L. Lunde, Ammonia Plant Safety. vol. 24, 1982.
26. A. Cracknell. AIChE Symposium, Safety in Ammonia Plants, 1982.
27. O. L. Towers, Metal Construction, 1984, p. 479.
28. T. Kawamoto, T. Kenjo, Y. Imasaka, IHI Engineering Review, vol. 10 No. 4, 1977, p. 17.
29. H. Spaehn, AIChE Svmposium, Safety in Ammonia Plants, 1982.
30. J. C. Guild, AIChE Symposium, Safety in Ammonia Plants, 1982.
 31. ASME SE-138, Standard Method for Wet Magnetic Particle Inspection.
32. L. Adams, AIChE Symposium. Safety in Ammonia Plants, 1982.

*Reprinted with permission from Materials Performance, Vol. 25, No. 12, December 1986, pp 18-22.
©1986, National Association of Corrosion Engineers Houston, TX. Reprinted text has been edited for
clarification and space requirements.

Editor's note: Some ASME Boiler and Pressure Vessel Code requirements may have changed because
of advances in material technology and/or actual experience. The reader is cautioned to refer to the latest
edition of the ASME Boiler and Pressure Vessel Code for current requirements.