Brasses with higher zinc (above 15%) in aqueous ammonia environments are prone to cracking.
Ammonia reacts with copper and zinc in the
presence of water and oxygen, forming complexes like copper-ammonia complexes. This reaction is more aggressive as zinc content rises
because zinc is less noble (more reactive) than copper, making higher-zinc brasses more vulnerable. The process often starts at stressed
24 areas—like welds or bends—where the alloyAPI is
RECOMMENDED
under tension.PRACTICE 571
Over time, tiny cracks form and propagate, potentially leading to failure.
3.4 Ammonia Stress Corrosion Cracking
3.4.1 Description of Damage
a) Aqueous streams containing ammonia may cause SCC in some copper alloys.
Anhydrous ammonia is pure ammonia (NH₃) gas, often stored as a liquid under
b) Carbon steel is susceptible to SCC in anhydrous ammonia. pressure, with no water involved. Normally, carbon steel does okay with anhydrous
ammonia—it’s why steel tanks and pipes are common for storing and moving it. But
high-strength steel can run into SCC.
3.4.2 Affected Materials
a) Copper-zinc alloys (brasses, especially as zinc increases above 15 %), including admiralty brass and
aluminum brasses, in environments with aqueous ammonia and/or ammonium compounds.
b) Carbon steel, especially high-strength steel, in anhydrous ammonia.
Anhydrous ammonia isn’t acidic or super corrosive on its own—it doesn’t eat steel like rust does. But when it’s in contact with
3.4.3 Critical Factors high-strength steel, it can sneak into those stressed spots or tiny cracks. If there’s even a little bit of oxygen (say, from air trapped
during filling) or other impurities in the ammonia, it sets off a reaction. The ammonia molecules mess with the steel at an atomic level,
weakening the bonds holding it together in those high-stress zones.
a) For copper alloys:
susceptible alloys may suffer cracking under the combination of residual stress and exposure to
ammoniated chemical compounds;
zinc content of brasses affects susceptibility, especially as zinc increases above 15 %;
a water phase with ammonia or ammoniacal compounds must be present;
oxygen is necessary, but trace amounts are sufficient;
pH needs to be above 8.5;
occurs at any temperature;
residual stresses from fabrication or tube rolling are sufficient to promote cracking.
b) For steel:
anhydrous ammonia with < 0.2 % water may cause cracking in carbon steel;
cracking has been reported as low as −27 °F (−33 °C) in laboratory testing; crack growth rates and
cracking susceptibility increase with increasing temperature, but cracking can occur at ambient or
refrigerated conditions;
stress relief after welding eliminates susceptibility of most common steels (those not greater than 70 ksi
minimum specified tensile strength);
contamination with even small amounts of air or oxygen increases tendency toward cracking;
high residual stresses from fabrication and welding increase susceptibility.
3.4.4 Affected Units or Equipment
a) Copper-zinc alloy tubes in heat exchangers.
Ammonia is present as a process contaminant in some services or may be intentionally added as an
acid neutralizer.
Ammonia can be present in cooling water.
Ammonia can be present in steam condensate and boiler feedwater (BFW) systems. Some chemicals
used for treating BFW, including hydrazine, neutralizing amines, and ammonia-containing compounds,
can lead to SCC if not properly controlled.
DAMAGE MECHANISMS AFFECTING FIXED EQUIPMENT IN THE REFINING INDUSTRY 25
b) Non-stress-relieved carbon steel ammonia storage tanks, piping, and equipment in ammonia refrigeration
units, as well as some lube oil refining processes.
3.4.5 Appearance or Morphology of Damage
a) Copper alloys.
Surface-breaking cracks may show bluish corrosion products.
Exchanger tubes show single or highly branched cracks on the surface.
Cracking can be either transgranular (Figure 3-4-1 and Figure 3-4-2) or intergranular (Figure 3-4-3),
depending on the environment and stress level.
b) Carbon steel.
Cracking will occur at exposed non-stress-relieved welds and HAZs.
Cracking is primarily intergranular in nature.
3.4.6 Prevention/Mitigation
a) Copper alloys.
Copper-zinc alloys with < 15 % zinc have improved resistance.
The 90-10 Cu-Ni and 70-30 Cu-Ni alloys have very low susceptibility. Below 120 °F (50 °C), the cupro-
nickels are immune for all practical purposes.
SCC in steam service can sometimes be controlled by preventing the ingress of air.
300 series SS and nickel-based alloys are immune.
b) Carbon steel.
SCC of steel can be prevented through the addition of small quantities of water to the ammonia (0.2 %
minimum). Be aware that vapor spaces could have less than 0.2 % water present due to partitioning of
ammonia in water phase.
An effective stress relief of the welds reduces residual stress to the point where ammonia SCC can be
prevented.
Low-strength steels (<70 ksi minimum specified tensile strength) should be used.
Prevent ingress of oxygen into storage facilities. Even low levels of oxygen (<5 ppm) have been reported
to lead to cracking under some conditions. Oxygen levels should be maintained below 1 ppm.
Nitrogen can be used to purge oxygen prior to introduction of ammonia into atmospheric and pressurized
storage systems.
3.4.7 Inspection and Monitoring
a) For copper alloys:
the pH and ammonia content of water draw samples should be monitored to assess susceptibility of
copper alloys to determine extent of inspection;
heat exchanger tubes can be monitored for cracking using ECT or VT. PT can be applied in the rolled
area, which is highly susceptible to cracking.
26 API RECOMMENDED PRACTICE 571
b) For carbon steel storage tanks (atmospheric or pressurized), vessels, and piping, in anhydrous ammonia:
WFMT is typically used on the welds and HAZs of storage tanks and pressure vessels and can also
identify SCC in piping; alternatively, eddy current array testing can be used to perform these inspections;
angle beam UT (SWUT or PAUT) can be performed from the outside surface;
AET can be used for locating cracks and monitoring crack growth in vessels.
NOTE NH3 SCC can occur parallel, transverse, or oblique to the weld and HAZ. NDE applied should be performed to
detect various orientations of SCC.
3.4.8 Related Mechanisms
None.
3.4.9 References
1. Corrosion Basics—An Introduction, NACE International, Houston, TX, 1984, p. 117.
2. ASM Handbook—Corrosion, Volume 13, ASM International, Materials Park, OH.
3. A. Cohen, “Copper and Copper-base Alloys,” Process Industries Corrosion—The Theory and Practice,
NACE International, Houston, TX, 1986, pp. 479–501.
4. NACE Publication 5A192, Integrity of Equipment in Anhydrous Ammonia Storage and Handling, NACE
International, Houston, TX, 2004.
5. “Environmental Cracking,” Materials Technology Institute, St. Louis, Missouri, 2016.
Figure 3-4-1—Ammonia SCC in an inhibited admiralty tube UNS C44300, 0.75 in.
diameter, BWG 16 (0.063 in. thick) with extruded fins.
DAMAGE MECHANISMS AFFECTING FIXED EQUIPMENT IN THE REFINING INDUSTRY 27
Figure 3-4-2—High-magnification view of a cross section of the tube in Figure 3-4-1
showing transgranular cracking. (Magnification 500X.)
Figure 3-4-3—High-magnification view of a cross section
of a brass exchanger tube showing intergranular cracking.
