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Definistion

According to the NACE Standard MR 0715-88 sour environment definition for general purposes of carbon
and low alloy steel. The definition states that 0.05-Psia or equal to 0.34 kPa partial pressure H2S in gas
phase will cause Sulfide Stress Cracking (SCC) for Carbon steel and low-alloy steels at low temperature.
And for liquid phase, the total sulfur content is more than 0.5% is called sour.
H2S is the biggest caused of corrosion in pipelines of sour field. Hydrogen sulfide reacts with ferrous to
form a H2S film, but as this film get dissolved more and more ferrous will be available to get attacked by
H2S. The pipeline become thinner and thinner and finally become unsafe to use. Stress Sulfide Corrosion
occurs when metal is in exposed to H2S and water. And it will generate atomic hydrogen between grains
of the metal and reduces metal ductility. Damage result by H2S corrosion:

 Sulfide Stress Cracking


 Blistering
 Hydrogen induced cracking
 Hydrogen embrittlement
In figure 1. We can see the schematical appeareance of damage mechanisms in sour service.

Hydrogen Induced Cracking


NACE MR0175 or ISO 15156 defined Hydrogen Induced Cracking (HIC) are planar cracking which
occurs in carbon and low alloy steels when atomic hydrogen diffuses into the steel and then combines to
form molecular hydrogen at trap sites with no external stress. Example of JIC can be seen in this figure
Sulfide Stress Cracking
Definition from NACE Standard MR0175 and ISO 15156, Sulfide Stress Cracking (SCC) is cracking of
metal involving corrosion and tensile stress (residual and/or applied) in the presence of water and H2S. the
results of this cracking can be seen in figure 3.

Figure 3.
Stress Oriented Stress Cracking (SOHIC)
NACE MR0175 and ISO 15156 defined SOHIC as staggered small cracks formed approximately
perpendicular to the principle stress (residual or applied) resulting in a “ladder-like” crack array linking
(sometimes small) pre-existing HIC Crack.

Figure 4.

Mechanism of H2S Corrosion


H2S Corrosion mechanism is a complex step reaction. Sour corrosion mechanism involve FeS formation,
Hydrogen gas formation, Hydrogen diffusion, Hydrogen trapping in defaults, increasing pressure and then
damage formation (SSC, Blistering, HIC and Hydrogen embrittlement). We can see the mechanism of
Hydrogen embrittlement formation in figure 2.
The overall reaction :
Fe + H2O + H2S FeSx + H2 + H2O
Half cell reaction at anode :
Fe Fe 2+ + 2e-
Half cell reaction at cathode :
H2S + 2e- H + + S 2-
H + + H + + 2e- H2

H2S is the agent which can trigger the corrosion process to happen as below step:
H2S H+ + HS- (1st dissociation reaction)
HS- H+ + S2- (2nd dissociation reaction)
Fe  Fe2+ + 2e- (Anodic/ oxidation reaction)
Fe2+ + S2-  FeS (precipitation of FeS)
H+ + e-  H0ads (Cathodic reaction/ adsorbed H-atom is adsorbed)
H0ads + H0ads  H2 (Cathodic reaction/ hydrogen gas is formed)
Temperature effect
Rule of thumb:
Most of the cases, for every 10ºC increase of temperature, corrosion rate of metal will be doubled.
Such for example, when corrosion rate of a metal is 10 mpy at 30ºC, it will be expected rise to 20
mpy at 40ºC (Materials Tech Inst, 2008)

Figure . General relation between temperature and corrosion rate.


Theoretically, temperature related to reaction rate constans of Arrhenius Equation as follows:
𝐶
𝐿𝑜𝑔 𝐾 = 𝐴 −
𝑇
Figure 4. Corrosion scale on different temperature for Carbon Steel (pH2S = 1.2 MPa, pCO2 =
0.6 MPa (a) 30ºC, (b) 60ºC, (c) 90º, (d) 120ºC
For short term exposure, H2S corrosion seems very weak and do not have an effect longer exposure
times in which corrosion rate is predominantly limited by the presence of iron sulfide scale. Hence,
temperature directly affected the morphology and composition of corrosion products (Figure 4)
which in turn caused the change of corrosion rate and occurrence of localized corrosion [Zhang et
al, 2011].
Oxygen content (concentration)
Mild steel and stainless steels 304 and 316 are most affected by the presence of O2. For stainless
steels, polarization resistance increases and corrosion rate decreases by an order of magnitude in
oxygen saturated solutions (temperature operation range: 20 - 80ºC)
This happen because oxide film on the surface of stainless steel cannot be formed without the
presence of oxygen. In the case of steel, the effect of oxygen is to combine with the iron to form
ferrous and ferric oxides which are not protective at the initial stages and thus accelerate steel
dissolution. Dissolved oxygen content would also increases as temperature increased (Pijanowski
et al, 1969).

H2S Partial Pressure (Gas System)


ANSI/NACE MR0175/ISO 15156 indicates that in production conditions with partial pressure of
H2S (ppH2S) below 0.3kPa (0.05psi) no special precautions are required for carbon and low alloy
steels. However highly susceptible carbon and low alloy steels (high strength, heavily cold worked
etc) can still be susceptible to H2S related damage mechanisms even at ppH2S below these limits.
For corrosion resistant alloys (CRAs) there is now ppH2S low limit, which means precautions
need to be taken whenever the possibility of H2S is present.

First, we have to define the partial pressure of H2S (ppH2S ) which is calculated as:

ppH2S = system total absolute pressure x mol fraction of H2S present

The partial pressure mentioned in Section 7.1.2 is the partial pressure of H2S in the gas phase in
equilibrium with the water in the production fluid. Annex C gives information on how to calculate
H2S partial pressure.

Notes:
X : mole fraction H2S in gas, % x 104 (parts per million by volume).
Y : Total absolute pressure, MPa
1 pH2S : 0.3 kPa
2 pH2S : 1 kPa
3 pH2S : 10 kPa
4 pH2S : 100 kPa
5 pH2S : 1000 kPa

Figure 1. Partial Pressure of H2S for different pressure.


Regions 1, 2, and 3, Figure 1, cover usual conditions above 0.3 kPa. Note 1 mentions the unknown
performance of steels above 1 MPa. The maximum partial pressure limit for carbon steels depends
on many variables as noted in 15156-2 Clause 6. Currently a NACE TM0177 test with 100 kPa
H2S, ~2.7 pH, room temperature, 50 g/L NaCl is considered to cover all normal production
conditions for carbon steels (NACE MR0175/ISO 15156-1 Item No. 21306, First Edition: 2001).

Figure 2. Effect of temperature on corrosion rate of steel (pH2S = 1.2 MPa coexist with pCO2 =
1.0 MPa)
For Carbon Steel, the effect of H2S partial pressure can be seen in Figure 3 below.
Figure 3. SEM Images of the corrosion scales formed under different H2S partial pressure at
60ºC; (a) 0.15 MPa, (b) 0.3 MPa, (c) 1.0 MPa, (d) 1.5 MPa, (e) 2.0 MPa, (f) 2.5 MPa (Adapted
from Zhang et al, 2011)

As shown in Figure 3, it is clear for constant temperature circumstances, higher pressure implied
to system prone to initiate corrosion rate and exhibits smaller molecular scale upon metal surface.
Hence, high pressure operation could establish pitting corrosion on the metal surface. Figure 5
represents relationship between reacted S and Cl atoms with metals on different depth of pit.
“0” point,
bootom pit.

Figure 5. (a) SEM image of Pitting Corrosion upon Carbon Steel surface.
Figure 5 proved that higher pressure applied would make S and Cl atom to more reactive and
reacted to metal (Fe) surface by following reaction:
Figure 6. Reaction pathway of H2S Corrosion [Adapted from Sun et al, 2007]

H2S environment could construct amorphous ferrous sulfide, mackinawite, and cubic ferrous
sulfide. Among those mentioned, mackinawite allegedly first formation during reaction upon steel
surface by direct reaction {Sun et al, 2007].

Concentration Effect
Indeed, H2S influence on the protective ability of sulfide film formed. As the concentration
increases, film formed rather loose even at pH 3 – 5 does not contribute to the corrosion inhibiting
effect [Shoesmith et al, 1980].

References
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and Engineering 4th Edition. A John Wiley & Sons, Inc., Publication. 2008. Hoboken.
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