Department of Metallurgical Engineering and Materials Science, IIT Bombay

Corrosion & Protection of Materials

[MM 454]

End-semester examination, April 2014

(Solutions)
Q1. Using the standard approximation,
for small values of x, show that for small
overpotentials, , the Butler-Volmer equation simplies to
. If = 0.5, z = 1, and T =
298 K, show that this approximation introduces an error of < 1% for < 0.01 V. [4]
nF ( E Ecorr )
(1 )nF ( E Ecorr )
inet icorr exp
exp

RT
RT

Ans: Butler-volmer equation

Using the approximation as given,

nF (1 )nF
inet icorr 1
1

RT
RT

or

nF (1 )nF
inet icorr

RT
RT

nF
i net icorr

RT

for = 0.5; R = 8.314 J/mol K; z = 1; T = 298K; & = 0.01;

inet = 0.3919i0
inet,2 =
inet,2 = 0.3894 i0
Error = inet - inet,2 = = (0.3919i0 - 0.3894 i0) *100 = 0.25 i0
The difference between the two values is < 1%

Q2. Two hypothetical metals (M1 & M2) are in contact with an aqueous medium where maximum
dissolved O2 concentration is 8.3 mM. Corrosion current density (icorr) of M1 and M2 are
0.032mA/cm2 and 0.32 mA/cm2, respectively. Using following data and Evans diagram explain the
nature of polarization occurring in these metals. Do = 10-5 cm2/s , n =2, = 0.5 mm.
[4]
Ans: max dissolved O2 conc. = Cbulk
= 0.83mM = 0.8310-3 moles/l = 0.8310-3 moles/1000cm3
maximum diffusion limited cathodic current =

iL i max

nFD0

Cbulk

Do = 10-5 cm2/s , n =2, = 0.5 mm

iL = 0.00032038 A/ cm2 = 0.32 mA/cm2
For M2, icorr = iL .
For M1, icorr is an order of mag. less than the iL.
Both metals are under activation polarization. But cathodic reaction is under activation polarization in case
of M1 and conc. polarization in case of M2.
Q3. A weathering steel specimen is exposed to a highly polluted, industrial-marine environment.
After one year of exposure, the penetration is 25 m, and after four years the penetration is 28
m. Assume that specimen penetration depth (p, m) follows bilogarithmic law with time (t, h):

, where A & B are constants. Calculate the following:

[4]
(a) The constants A and B
(b) The average corrosion rate, in terms of penetration per year, over a 40 - year period, assuming
that environmental conditions do not change signicantly during this time period.
(c) The instantaneous corrosion rate, in terms of penetration per year, at 5, 25, and 40 years of
exposure.
1.54
40

1.52
A = 1.397
B = 0.081

linear plot
35

1.48
1.46

p, m

Log p , m

1.50

1.44

30

1.42
25

1.40
1.38
-0.2 0.0

0.2

0.4

0.6

0.8

1.0

Log t, year

1.2

1.4

1.6

1.8

20

Ans:

10

20

30

40

50

t, year

From data for 1 an 4 years, constants A & B can be calculated; i.e. A = 1.397; B = 0.081;
t = 40yr;
log(p40) = A + B*Log10( t ) = 1.526
p40=10^logp40 = 33.63um
for t5=5yr;
log(p5) = A + B*Log10( t5 ) = 1.45361657
p5=10^logp5 = 28.419um
for t25=25yr; log(p25) = A + B*Log10( t25 ) = 1.510233141
p25=10^logp25 = 32.376um
Average penetration/ yr, for 40 yrs = (33.6-0)um/(40-0) = 0.84 um/yr
Instantaneous corrosion rate in penetration / year
PE5 = 28.419/ 5 =5.6838 um/ yr
PE25 = 32.376/25 = 1.295 um/ yr
Q4. Explain why:

[4]

i) Acidity is developed within a pit. : During propagation stage accumulation of M+ ions in pit attracts
more anions (e.g. Cl-) into the pit and they form MCl salt. MCl reacts with H2O (i.e. hydrolyses) to form
acid in pit
MCl + H2O MOH + HCl
[this is called hydrolysis]
Formation of HCl reduces pH inside the pit and acidity develops.
ii) Pitting reaction is sustained even after oxygen is consumed: Propagation stage of the pitting
process is autocatalytic, in the sense that, because of Cl- ions and the hydrolysis process, acidity develops
and that propels the corrosion in pit. More corrosion, more Cl- in pit, which leads to further acidity and
further corrosion. Thats how reaction is sustained even though O2 is consumed completely.

iii) Pitting attack is decreased by an increase of velocity of corroding uid: A moving fluid washes
away the acid inside the pit and prevents the autocatalytic process to ensue. This may lead to re-passivation
in pit, which is otherwise impossible in a stagnant situation.
iv) why Mo imparts better pitting resistance to steel in presence N in steel composition: Mo forms
passivating MoO2 in acid condition of the pit (i.e. lower the icrit). In presence on N and in very alkaline
condition MoO42- form, which act as a buffer for Cl- ions. The role of N is to release NH4+ ions to make
environment alkaline for easy formation of MoO42-.
Q5. Following observations were made from microscopic observations of fractrographs different
samples. Explain whether SCC, corrosion fatigue, hydrogen induced cracking or any combination
of them is the cause of the failure:
[5]
i) alloy under constant stress, transgranular branched cracks, sharp crack tip : A sign of SCC, as the
material is under constant load, transgranular crack means the mechanism might be hydrogen induced
cracking.
ii) pure metal under tensile stress with superimposed cyclic stress, blunt crack tip, transgranular
unbranched crack. : Tensile cyclic stress, TG un-branched crack implies crack due to corrosion fatigue.
iii) high-strength alloy, transgranular branched cracks, sharp crack tip, room temperature failure:
high-strength alloy with transgranular branched cracks, sharp crack tip, room temperature failure implies a
SCC
iv) alloy under constant stress, Intergranular branched cracks, sharp crack tips, high temperature
failure, corrosion products in the cracks: SCC due to precipitation or depletion in GB, resulting in
preferential corrosion along GB. Corrosion product in cracks indicates an active path dissolution
mechanism.
v) highly-cold-worked alloy, Intergranular unbranched cracks, sharp crack tip, room temperature
failure: highly-cold-worked alloy high residual stress, Intergranular crack active path dissolution
mechanism
Q6. Using an Evans diagram compare and explain the rate of crevice corrosion in following three
cases. Which of these cases will have the greater weight loss per unit area? Assume the crevice
area is same in all.
[4]

Ans: Crevice area is same, but the exposed area is different, which increases in C > B > A. Correspondingly,
the limiting current for oxygen reduction
also increases in the same order. With the
area of the internal creviced metal being
constant in all cases, the corrosion current
density for the metal within the crevice
increases linearly (unfavourable area ratio).
The situation is explained in Evans diagram
below:

Q7. Ni high temperature oxidation is given as,

[4]

(a) Derive expression for critical partial pressure of O2

Ans: free energy of formation of oxide,

---------(1)

Equilibrium constant, K = aNiO / aNi * PO21/2 = 1 / PO21/2 (as activity of pure materials =1)
Now, eqn. 1 becomes,
; if O2 partial pressure is below this, then oxdn. not possible.
(b) Calculate the weight gain at 1,298 K after 20 h of oxidation.
Ans: Given, the parabolic rate constant, the oxdn. follows parabolic rate law, i.e.
, where y is
thickness or weight gain, k parabolic rate constant, t is time
After 20 hrs @ 1298 K, weight gain, y = sqrt(3.5 1010 g2cm4s1 * 20 * 3600s) =0.005 g/ cm2
(c) Calculate the oxide thickness (in m) after 20 h oxidation if NiO density is 6.67 g/cm3
Ans: after 20 hrs @ 1298 K, weight gain, y = 0.005 g/ cm2
Thickness, d = weight gain/ density = 7.610-6 m = 7.6 m
The parabolic rate constant was determined to be 3.5 10 10 g2cm4s1 for a Ni at 1,298 K.
Q8 Answer briefly:

[21]

(a) If by applying a cathodic current, the time to failure decreases and increases by anodic
polarization, explain which mechanism of SCC is suggested.
Ans: If time to failure decrease by increase in cathodic current, the hydrogen migrated into the
microstructure may be playing a role, i.e. the mechanism of scc may be controlled by hydrogen
embrittlement. More icathode, more hydrogen in lattice and that decrease time to failure. If by anodic
polarization time to failure increases, the mechanism may be active path dissolution, which is may be
hindered by passivation at the crack front, when the metal is anodically polarized.
(b) Explain beneficial/detrimental effect of following alloying elements in steel concerning its
corrosion resistance: Cr, Ni, Mo, N, Ti, Nb, S, P, B & C
[3]
Ans: Passivity & Pitting corrosion resistance: Cr, Ni, Mo decrease icrit for passivation and hence shift the
Epit to more positive value imparts pitting resistance. However, S decreases icrit and hence shifts Epit
negative. This detrimental effect also enhance if S forms MnS, which cause pitting in SS.
Mo adds to the pitting resistance of Cr in steel. Mo in presence of N is also very effective in pitting
resistance.
Crevice corrosion: Cr, Ni, Mo, and N improves resistance of stainless steels to crevice corrosion, because
they render good passivity to the steel.
IGC: S, P, B & C impurities can segregate to GB and make steel susceptible to IGC. C can form carbides
with Cr, sensitize the alloy and enhance IGC susceptibility. Ti & Nb improves IGC resistance by
stabilization; i.e. thery are more avid carbide former than Cr, and that how decrease sensitization in steel.
SCC: most elements/impurities that make steel susceptible to IGC also make it vulnerable to SCC.
(c) How hydrogen blistering takes place?

Ans: Atomic hydrogen enters the lattice from several sources, such as from cathodic hydrogen reduction.
This atomic hydrogen usually attracted towards high-energy sites such as vacancy, inclusions, flaws or tip of
micro-cracks. At these sites, H atoms combine to form H2 gas. Because of hydrostatic pressure of the H2 gas,
metal swells at that points and cause blistering.
(d) A gray cast iron pipe, used in the natural gas distribution system for a city, fails and leaks, even
though no corrosion is noticeable to the naked eye. Explain why the pipe failed.
Ans: The circumstances suggest graphitic corrosion, that is, the selective leaching of Fe from the lattice,
leaving behind the graphite flakes in the gray iron (these are corrosion products), which are not visible to
naked eye. Although the pipe appears to be sound, the attacked area is weak, porous, and spongy (due to
formation of graphitic carbon). The natural gas can leak through the area of graphitic corrosion and
eventually cause gas accumulations leading to an explosion.
(e) High-carbon steel leaf springs for an automobile are formed by hot working and cold working?
Explain which forming process is best for high corrosion resistance.
Ans: If formed by cold working, residual stresses are likely to be introduced into the springs, leading to a
stress cell and increase SCC susceptibility of the spring.
Hot-forming the springs will reduce the level of any residual stresses introduced into the spring and
minimize the stress cell and hence SCC susceptibility. However, the steel will contain ferrite and pearlite
(forming a composition cell), not to mention grain boundaries, inclusions, and other potential sites for
corrosion cells. Corrosion is still likely to occur even if the springs were produced by hot working.
(f) Sheets of annealed nickel, cold-worked nickel, and recrystallized nickel are placed into an
electrolyte. Arrange them increasing order of corrosion resistance and explain.
Ans: The cold worked nickel sheet is expected to have the poorest corrosion resistance due to the residual
stresses introduced during the cold working process.
The annealed nickel sheet should be most resistant to corrosion; the grain size is expected to be particularly
large and no residual stresses are expected; consequently a stress cell is unlikely. In addition, the annealed
sheet is expected to have the most uniform composition, that is, the least segregation, so a composition cell
is also unlikely.
The recrystallized nickel sheet should have intermediate corrosion resistance; the residual stresses should
have been eliminated as a result of the heat treatment but the grain size may be smaller than in the annealed
sheet.
(g) A brass plumbing fitting produced from a Cu-30% Zn alloy operates in the hot water system of
a large office building. After some period of use, cracking and leaking occur. On visual
examination no metal appears to have been corroded. Offer an explanation for why the fitting
failed.
Ans: Dezincification appears to be a logical explanation. The high zinc brasses are susceptible to
dezincification, and more so when the temperature is high, as in the hot water supply of the building. One of
the characteristics of dezincification is the formation of porous Cu layers in the regions that are attacked,
obscuring the damage. However, the porous copper layer is spongy, brittle, and weak, permitting the fitting
to fail and leak.
(h) Discuss advantage/disadvantage of sacrificial and noble coating.

Ans: Sacrificial coating can protect the steel even if the coating is removed, as it always acts as anode. In
case noble coating, if a minor defect appears, the base metal, which is anode, is exposed. Because of
unfavourable area ratio corrosion of base metal is faster and hence more damaging.
(i) What is age hardening? How it affect the SCC in aluminium alloys?
Ans: The age-hardening of alloys are the processes to promote a sub-microscopic precipitate of intermetallic
compound particles highly dispersed within the crystals, by a suitable sequence of heat-treatments. Its
function is to obstruct the movement of dislocations in the lattice and thereby harden and strengthen the
metal.
However, if some larger precipitate nucleate and grow at the grain boundaries (due to over aging or by
preferential growth), resulting in precipitates aligned along the grain boundaries. This leads to formation of
depletion zones adjacent to the grain boundary which may be more prone to attack than the grain boundary
region or matrix. This, thus, established a continuous active paths along the grain boundary, making the
more susceptible to SCC.
(j) Using Evans diagram, explain if cathodic protection is easier in acid medium or aerated neutral
medium.
Ans: in acid medium the cathodic reaction is H2 evolution (activation polarized) and in aerated neutral
medium the cathodic reaction is O2 reduction (conc. polarized). As is from the Evans diagram below, for
aerated neutral medium the current requirement is limited by limiting current (iL) which is always lower than
that in the case H2 evolution (activation polarized). Therefore, the current require for the cathodic protection
in aerated neutral medium is lower than that in the acid medium, i.e. cathodic protection is easier in aerated
neutral medium.

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