Corrosion of Stainless Steels

U. K. Chatterjee
Former Professor. IIT Kharagpur

1. “Stainless steels are not the solution to all corrosion problems”. Stainless steels do not rust in
normal atmospheric exposures, in natural waters and in oxidizing acids. But they corrode in
reducing acids. In chloride containing media they undergo localized corrosion like pitting,
crevice corrosion, intergranular corrosion and stress corrosion cracking.

2. Stainless steels derive their corrosion resistance to passivity. Passivity is achieved with the
addition of a minimum of 12% Cr. Nickel, molybdenum, copper enhance general corrosion
resistance in sulphuric acid. Mo imparts pitting corrosion resistance. Ti, Nb and Ta are added to
combat intergranular corrosion of austenitic stainless steels.

3. The phenomenon of passivity was first demonstrated by Faraday. He attributed passivity to

the iron oxide film formed on the surface of metal on exposure to hot concentrated nitric acid.
Once formed, its slow dissolution in this environment then determines the corrosion rate of the
metal.

4. The passive state is not an inert or static state, but a dynamic condition in which there is
continuous dissolution and repair of the passive film at discrete points in the surface.

5. Findings of Monnartz on passivity of Fe-Cr alloys (1911):

Low-chromium alloys with 12.5% or more chromium are resistant at room temperature to nitric
acid at all concentrations. With 14% Cr or more, Fe-Cr alloys resist such solutions at
temperatures up to boiling.

In reducing acids, additions of chromium to iron increase the rate of corrosion.

Mo additions increase resistance in nitric acid containing chloride salts.

Passivity depends on a source of oxygen, either from a compound in solution or from dissolved
oxygen gas.

In solutions in which a given Fe-Cr alloy e.g. nitric acid containing a chloride salt, passivity can
be induced by contacting the specimen with a platinum wire, adding platinum as alloying
element, or making the Fe-Cr alloy an anode by means of a cathode and an external EMF
(anodic protection). All of these procedures change the potential of the alloy in the noble
direction.

6. Some elaboration on Passivity

The Role of Alloying Elements
General Corrosion in Acids

Chromium

1. The minimum concentration of chromium required for passivity is a function of the type of
acid, its concentration and temperature. Thus, there is no fixed ratio of iron to chromium
concentration in Fe-Cr alloys that characterizes the passive state.

2. In practice, an alloy with 14-18% Cr provides resistance in a number of acid environments

Table 3, Uhlig). In boiling 65% nitric acid, Type 430 shows a corrosion rate of 0.5 mm per year
where carbon steel 1020 shows a rate of 4500 mm/year. In 10% sulphuric acid, however, rate is
6400 mm/year and in 1% HCl, the rate is 1500 mm/year. Higher Cr content, as in Type 446 (23-
27%Cr), gives still better performance.

3. The effect of Cr concentration on corrosion of iron in an oxidizing environment is shown in

Fig 1 (Uhlig). In boiling H2SO4 with ferric sulphate, the passive rate is reduced by 99% as the Cr
content is increased from 12 to 25%. Ferric sulphate addition raises corrosion potential from -
0.6 V to +0.6 V.(Table 2, Uhlig)

Ferric sulphate promotes passivity through a cathodic reaction of reduction of ferric to ferrous
ion (Fe+3 + e  Fe+2), with anodic dissolution of Fe, Cr and Ni (Fe Fe+2 + 2e). Hydrogen
evolution reaction follows when all of ferric sulphate is used up.

In active state, the alloy shows an increase in rate of corrosion (in 5% H2SO4) by a factor of 3
with increasing Cr from 10 to 35%.(Fig 1)

Nickel

1. Both in oxidizing and reducing acids, nickel addition may actually increase the corrosion rate
of Fe-Cr alloys. Fig 1 shows that 10% Ni alloy with <16% Cr have higher corrosion rates than the
alloy with no nickel. Only when Cr is increased to >16%, there is a rapid reduction in corrosion.

Thus in the presence of 10% Ni , increasing Cr >16% reverses the deleterious effect of Cr,
indicating that at these concentrations there is a synergistic effect between Cr and Ni on the
rate of hydrogen evolution corrosion (active state).

2. The beneficial effect of Ni in higher Cr alloys is evident from Fig 3 (Uhlig). Corrosion rate of 18
Cr- 8 Ni (Type 304) is appreciably lower than those of 16% Cr alloy (Type 403) or even 25% Cr
alloy (Type 446).
To provide a wider range of resistance to corrosion in sulphuric acid and sea water, 4% Ni is
added to 28 Cr-2 Mo and 2% Ni to 29 Cr-4 Mo new ferritic stainless steels.

3. Corrosion rate of Type 304 increases with increased concentration of sulphuric acid. (Fig 2,
Uhlig)

Molybdenum

1. Molybdenum enhances passivity of stainless steels in chloride environments. Corrosion

resistance of Type 304 steel enhances with addition of 2.5% Mo (Type 316). Since Mo is a ferrite
former, Ni content is increased by 3% in the alloy that could contribute to resistance.

2. Like nickel, molybdenum converts chromium into a beneficial alloying element in reducing
acids. But there is no significant effect on corrosion in oxidizing acids or solutions.

3. Mo contributes to resistance to pitting of austenitic stainless steels in chloride containing

media. All new ferritic alloys contain molybdenum (1 to 4%), primarily for increasing resistance
in sulphuric acid and to pitting.

Noble metals

Addition of noble metals like Cu, Pt, Pd in small amounts decrease corrosion rate of stainless
steels drastically.(Figs 5 & 6, Uhlig text) This is related to the low hydrogen overvoltage of these
metals.

Cr-Ni-Mo-Cu alloy (Alloy 20)

1. To provide resistance in broader ranges of concentrations and temperatures of sulphuric acid

solutions, Ni content of Type 316 was increased from 11 to 20% and 2.2% Cu was added. A
similar type alloy, 20 Cr-29 Ni- 2.25 Mo- 3.25 Cu, was developed by Fontana.

Mo enhances resistance at sulphuric acid concentrations between 20 and 70%, while Cu

provides resistance at concentrations <20% and >70%. Increasing Ni contributes resistance over
the entire range of up to 75% acid.

The alloy also performs well in oxidizing acids and solutions.

2. To combat SCC in sulphuric acid in the range of 20 t0 80%, nickel was increased in the alloy
from 29 to 40% (Carpenter 2 Cb -3 alloy). This alloy is usable in all aggressive environments,
only next to nickel-based Hastelloy alloys in performance.
Pitting and Crevice Corrosion

1. Description of pitting and crevice corrosion phenomena

2. Chloride salts impair the passive state of iron-chromium alloys. Depending upon the factors
involved in the passivity breakdown and the morphology of the subsequent attack, localized
corrosion can be classified as pitting or crevice corrosion if a chemical micro- or macro-
heterogeneity is developed at the metal/solution interface.

3. Mo addition to Type 304 and new ferritic alloys imparts resistance to pitting and crevice
corrosion. (Fig 18, Uhlig) Further increase in pitting resistance is obtained by addition of 2% Si
to Type 316 and by addition of 0.2% nitrogen to 23 Cr-4 Ni steel.

4. Prior passivation of the surface in a hot nitric acid-dichromate solution reduces the incidence
of pitting. Lowering of carbon content (Type 316 vs Type 316L) of passivated steels reduces the
incidence of pit initiation even further.

5. SP-2, a Type 316L steel with 2.5% Si and 0.23% N shows significant resistance to pitting and
crevice corrosion.

6. Measurement of critical pitting potentials (CPP or Epit) are used to determine resistance to
pitting. However, such rapid measurements are not reliable for long-time service. Pitting attack
has been observed in long-time exposures at potentials below the CPP.

7. Pitting Resistance Equivalent Number (PREN) for a stainless steel illustrates its resistance to
pitting corrosion and is denoted in terms of its alloy content: %Cr + 3.3% Mo + 16% N. (Fig 4a,
Rana et al)

PREN value of 32 is considered to be the minimum requirement for marine environment where
the concentration of chloride ion is above 2%. Duplex grades mostly satisfy this requirement.
(Table 7, Uhlig and Fig 4a Rana)

Seawater above 70 C demands the duplex grades. (Fig 4b, Rana) Pitting potential for duplex
grade steels are higher compared to Type 304 and Type 316.(Fig 5, Rana)

Intergranular Corrosion

1. Description of intergranular corrosion phenomenon

2. Carbon combines with chromium during exposure of the steels in the range of 500 C to 875 C
in austenitic stainless steels. Such exposures are involved during welding and during fabrication.
So, the term ‘weld decay’. A precipritate of chromium carbide(Cr23C6) forms preferentially at
the grain boundaries causing depletion of chromium. This is called ‘sensitization’. Decrease in
chromium leads to increase in corrosion rate.(Fig 4, Uhlig)

3.Nitrogen also reacts with chromium and forms β-Cr2N at the grain boundaries.

4. In ferritic stainless steels, the sensitization range is above 920 C, where the solubility of
carbon and nitrogen becomes significant in ferrite. Because of the difference in sensitizing
temperature range, the zones of intergranular corrosion in ferritic stainless steels are adjacent
to the welds.

5. Carbide particles nucleate at grain boundaries and grow into the metal grains on parallel
crystallographic planes, (Fig 7, Uhlig)

6. Immunity to intergranular corrosion is restored by heating the sensitized steel between 650-
815 C for a short time. As the diffusion of chromium in the bcc lattice of ferritic steel is
significantly higher than in austenitic steel, a uniform chromium composition is reestablished.

7. Reduction of interstitials is an effective means for reduction of susceptibility. For 18 Cr-2 Mo

alloys to be immune to intergranular corrosion, the maximum level of C+N is 60-80 ppm.
Ferritic stainless steels stabilized with Ti or Nb have also been developed.(Table 7, Uhlig)

8. Duplex grades have low carbon content (0.03%) and are not prone to intergranular corrosion.

Stress Corrosion Cracking

1. Description of stress corrosion cracking phenomenon

2. Austenitic stainless steels are susceptible to SCC in chloride (boiling MgCl2 or NaCl)
solutions.(Table 6, Uhlig)

3. Increasing Ni above or below 8% in Fe-18 Cr alloys increases resistance to SCC.(Fig 12A,

Uhlig)

4. Ferritic stainless steels are, in general, resistant to chloride SCC, but are susceptible when in
sensitized state or when they contain Ni >1%. In new ferritic alloys with high Cr and Mo,
cracking time in MgCl2 is rapidly reduced as Ni content exceeds 0.5% (Table 9, Uhlig), but these
alloys are resistant to SCC in NaCl solutions.

5. Duplex stainless steels have better resistance to SCC than austenitic grades. (Fig 8, Uhlig)