Material Science

Prof. Satish V. Kailas

Associate Professor
Dept. of Mechanical Engineering,
Indian Institute of Science,
Bangalore – 560012
India

Chapter 13. Corrosion and Degradation of Materials

What is degradation?
What are the mechanisms of degradation?
What is corrosion and how does it degrades the material?
How the corrosion tendency for a metal is quantified?
What is passivity?
What are the types of corrosion?
What is the role of hydrogen in material degradation?
What is the effect of corrosion on ceramics?
What is the effect of corrosion on polymers?
Want to know how good you are in the subject?

What is degradation?
Engineering materials are subjected to numerous external mechanical and
environmental factors during their service. Those factors include temperature, chemical
attack, mechanical vibration, applied mechanical loads, etc. Under the influence of these
factors the engineering materials loss their potential to perform the intended task.
The degradation is inevitable, and may lead to catastrophes! Hence, degradation
of materials not only be monitored but also be factored into the design of different
components by engineers.

What are the mechanisms of degradation?

Mechanism of degradation is different for each engineering material group.
Material loss either by dissolution or by formation of nonmetallic scale/film occurs in
metals, while ceramics are relatively resistant to degradation. However, ceramics also
gets deteriorated at extreme temperatures. Polymers, on the other hand, may
dissolve/distort in presence of a liquid solvent or even when exposed to electromagnetic
radiation. Degradation due to chemical/electro-chemical factors is termed as corrosion,
while oxidation refers to formation of nonmetallic scales in metals.
What is corrosion and how does it degrades the material?

Corrosion can be defined as unintentional deterioration of materials due to

electrochemical factors. It usually starts at the external material surface. The corrosion
resistance of metals and alloys is a basic property related to the easiness with which these
materials react with a given environment. Corrosion is a natural process that seeks to
reduce the binding energy in metals, and is of electrochemical in nature. The end result of
corrosion involves a metal atom being oxidized, whereby it loses one or more electrons
and leaves the bulk metal. The process is called oxidation, some times also called anodic
reaction. The lost electrons are conducted through the bulk metal to another site where
they are reduced, the process called reduction. The site where metal atoms lose electrons
is called the anode, and the site where electrons are transferred to the reducing species is
called the cathode. As a consequence of these electrochemical reactions, metal ions either
go into the corroding solution as ions, or they may form an insoluble compound with
nonmetallic elements.

How the corrosion tendency for a metal is quantified?

Corrosion tendencies for different metals in measured in terms of electromotive

force (EMF). A series of metals are arranged according to their potential to get corroded
with respect to hydrogen electrode. Table13.1 presents EMF series, and those at top are
noble, while those metals at bottom are more prone to corrosion than the metals above
them in the series.

Table 13.1: Standard EMF series of metals.

Metal Electrode potential, E0 (V)

Au → Au3++3e- +1.420
2H2O → O2+4H++4e- +1.229
Pt → Pt2++2e- +1.200
Increasingly inert ↑ Ag → Ag++e- +0.800
Fe2+ → Fe3++e- +0.771
4(OH)- → O2+2H2O+4e- +0.401
Cu → Cu2++2e- +0.340
H2 → 2H++2e- 0.000
Pb → Pb2++2e- -0.126
Sn → Sn2++2e- -0.136
Ni → Ni2++2e- -0.250
Co → Co2++2e- -0.277
Cd → Cd2++2e- -0.403
Fe → Fe2++2e- -0.440
Cr → Cr3++3e- -0.744
Zn → Zn2++2e- -0.763
Al → Al3++3e- -1.662
Increasingly active ↓
Mg → Mg2++2e- -2.363
 Na → Na++e- -2.714
K → K++e- -2.924
Li → Li++e- -3.050

As corrosion is electrochemical in nature, temperature and concentration of chemical

does have an important role to play. In general, with increase of either or both
temperature and concentration, corrosion rate increases. The electrode potential depends
on the concentration of the electrolyte. At 25˚C, the following equation, known as Nernst
equation, gives the electrode potential:

0.0592
E = E0 + log(C ion )
n

Where E is the electrode potential in a solution containing a concentration Cion (in moles)
of metals, n is the valence of the metallic ion, E0 is the standard electrode potential in a 1-
M solution.

Galvanic Series
Anodic or Least Noble end
Magnesium
Magnesium Alloys
Zinc
Aluminum 5052, 3004, 3003, 1100, 6053
Cadmium
Aluminum 2117, 2017, 2024
Mild Steel (1018), Wrought Iron
Cast Iron, Low Alloy High Strength Steel
Chrome Iron (Active)
Stainless Steel, 430 Series (Active)
302, 303, 321, 347, 410,416, Stainless Steel (Active)
Ni - Resist
316, 317, Stainless Steel (Active)
Carpenter 20cb-3 Stainless (Active)
Aluminum Bronze (Ca 687)
Hastelloy C (Active) Inconel 625 (Active) Titanium (Active)
Lead - Tin Solders
Lead
Tin
Inconel 600 (Active)
Nickel (Active)
60 Ni-15 Cr (Active)
80 Ni-20 Cr (Active)
Hastelloy B (Active)
Brasses
Copper (Ca102)
Manganese Bronze (Ca 675), Tin Bronze (Ca903, 905)
Silicone Bronze
Nickel Silver
Copper - Nickel Alloy 90-10
Copper - Nickel Alloy 80-20
430 Stainless Steel
Nickel, Aluminum, Bronze (Ca 630, 632)
Monel 400, K500
Silver Solder
Nickel (Passive)
60 Ni- 15 Cr (Passive)
Inconel 600 (Passive)
80 Ni- 20 Cr (Passive)
Chrome Iron (Passive)
302, 303, 304, 321, 347, Stainless Steel (Passive)
316, 317, Stainless Steel (Passive)
Carpenter 20 Cb-3 Stainless (Passive), Incoloy 825nickel - Molybdeum - Chromium -
Iron Alloy (Passive)
Silver
Titanium (Pass.) Hastelloy C & C276 (Passive), Inconel 625(Pass.)
Graphite
Zirconium
Gold
Platinum
Cathode Or Most Noble end

Faraday’s equation gives the amount (w, weight in gms.) of metal plated on the cathode,
or removed from the metal by corrosion:

ItM
w=
nF

where I is the current (A), M is the atomic mass of the metal, n is the valence of the metal
ion, t is the time (secs), and F is the Faraday’s constant (96,500 C).

What is passivity?

Under particular environments, some active metals and alloys may turn inert,
known as passivity. It is usually observed in metals such as Cr, Fe, Ni, Ti and their alloys.
Passivity is inherited as a result of formation of a thin and highly adherent oxide film on
the metal surface. For example: stainless steels are highly resistant to corrosion in many
environments, except in hard sea water. For steels, Cr forms a protective layer.
Aluminium is also observed to passive in many environments. This is due to formation
thin oxide layer.

What are the types of corrosion?

Corrosion in metals is classified based on the manner in which it is manifest into

eight forms, namely: uniform, galvanic, crevice, pitting, inter-granular, selective
leaching, erosion-corrosion, and stress corrosion.

Uniform corrosion: As the name suggests, electrochemical corrosion occurs over entire
exposed surface with equal intensity. It usually results in formation of a scale/film. This
form of corrosion is most common, easy to monitor, and less damaging than the other
forms. Painting the surface is best counter measure for it.
Galvanic corrosion: This occurs when two metals with different compositions i.e. EMF
are electrically connected in presence of an electrolyte. Out-of-these two metals, less inert
metal will corrode, while the other will be protected from the corrosion. Corrosion rate
depends on the relative anode-to-cathode surface areas that are exposed to the electrolyte.
the following measures are observed to reduce the damage due to this form of corrosion:
when coupling of two different metals is unavoidable, choose that are close together in
EMF series; tailor the anode-to-cathode area ratio; metals may be electrically insulated
form each other; or use a third metal to protect the both, known as cathodic protection.

Crevice corrosion: This occurs as a result of concentration difference between two

regions of same metal component. Corrosion takes place in the locale that is of lower
concentration. Probable sites for this corrosion are: crevices and recesses, under scales of
dirt/corrosion product. This form of corrosion may be avoided if enough care is taken to
avoid concentration differences. E.g.: welding instead of riveting. Other measures include
removing accumulated deposits; avoiding stagnant areas.

Pitting: It is another form of localized corrosion. As a consequence of this, small pits, and
holes form, hence the name. This occurs in normal direction to the surface exposed, and
so is difficult to monitor. Thus, it is extremely dangerous form of corrosion, as material
loss is often undetectable till the component fails. Same measures as for crevice corrosion
are part of care against this form of corrosion. In addition, polishing of surfaces could do
good.

Inter-granular corrosion: This occurs again due to concentration difference, but now
along grain boundaries, which are usually of different chemical composition compared
with rest of the grains. Thus grain boundaries are highly susceptible to corrosion. This
form of corrosion is very severe in stainless steels. These materials may be protected by
suitable heat treatment; lowering carbon content; addition of alloying elements those
readily forms of carbides.

Selective leaching: It is the preferential removal of a solid alloy by corrosion process.

Best example can be dezincification of brass. It also occurs as the loss of Ni, Sn and Cr
from Cu-alloys; Fe from cast iron; Ni from steel alloys, and Co from satellite. As a result
of this corrosion, mechanical properties of the components are impaired as the
component becomes porous. Measures of protection include change if composition;
change of environment; use of cathodic protection.

Erosion-corrosion: It is defined as acceleration of corrosion attack in a metal due to

relative motion of a corrosive fluid and a metal surface i.e. is result of combined action of
chemical attack and mechanical abrasion/wear. Practically, all metals and alloys are
prone to this corrosion form. It has more damaging influence on metals which passivate
by forming a protective film and also on soft metals like Cu and Pb. Counter measures
include: change of design; choosing different metal for the component; removal of
particulates and bubbles form the fluid to lessen the erosive effects.
Stress corrosion: This form of corrosion, also known as stress corrosion cracking (SCC),
occurs as a result of combined action of applied tensile stresses and corrosive
environment. During SCC, the metal’s surface is usually attacked very little while highly
localized cracks propagate through the metal section. The stresses which cause SCC can
be residual or applied. Only certain combinations of alloys and environments cause SCC.
E.g.: Stainless steels crack in chloride environments but not in ammonia-containing ones.
Best counter measure is elimination of external stress. Other measures are: to eliminate
detrimental environment; change of the alloy if neither environment nor stress level can
be changed; cathodic protection: addition of inhibitors.

What is the role of hydrogen in material degradation?

Hydrogen embrittlement is on of the degradation mechanism in material failure.

Here, atomic hydrogen produced during corrosion diffuses interstitially through crystal
lattice, and interferes with dislocation motion, leading to failure. It is similar to stress
corrosion in the sense that ductile materials experience brittle failures as a result. Counter
measures to hydrogen embrittlement include: heat treatment to reduce strength of the
alloy; removal of source of hydrogen; baking the component to drive out any dissolved
hydrogen.

What is the effect of corrosion on ceramics?

Ceramics, being compounds between metallic and nonmetallic elements, may be thought
of as having already been corroded. It is often said that one of the biggest advantages
which ceramics have over other engineering materials is their corrosion resistance, that is,
their chemical inertness in corrosive environments.

Corrosion is generally understood as property degradation due to environmental attack.

Ceramics corrode by simple chemical dissolution, in contrast to the electrochemical
processes involved with corrosion of metals. There are a number of environments in
which ceramics can degrade at a rapid rate. There exists a tremendous need for reliable
and corrosion resistant structural ceramic or partly ceramic materials which can be used
in aggressive environments such as:

- High energy battery systems (such as sodium-sulphur): beta-alumina is being

investigated

- Gas turbines: silicon nitride and/or carbide are being investigated

- Heat exchangers: SiC, composites are being investigated

Ceramics are indeed much more environmentally stable, as compared to any other group
of engineering materials, e.g. metals or plastics. Still, the potential for ceramics as
corrosion resistant engineering structural materials are far from being fully realized,
because of:
- Mechanical non-reliability of structural ceramic components

- Difficult design with brittle materials

- A shortage of information and standardization of ceramics

- Human reluctance to use non-ductile materials

What is the effect of corrosion on polymers?

While the plastics industry searches for solutions to the problem of plastics waste, there
is, surprisingly, a growing band of people trying to save plastics. The crucial fact is that
plastics are organic and can are prone to physiochemical attacks. Polymeric materials
degrade by non-corrosive processes.

As all other engineering materials, plastics do indeed degrade during their service.
However, degradation of plastics is not termed as corrosion, as it is of physiochemical in
nature in contrast to electrochemical corrosion of metals. Degradation of polymers, thus,
involves a wide variety of reactions and results like absorption and swelling, dissolution,
bond rupture due to heat, chemical effects, or radiation; weathering, etc. Degradation of
polymers might be due to exposure to light (especially UV), humidity, oxygen, heat,
bacteria or external loads/stress. However, due to complex nature of chemical bonds in
polymers, their degradation mechanisms are not well understood.

Swelling and dissolution: Polymers, when exposed to liquids, they get swelling as a
result of solute diffusion and absorption of solute. Because of swelling i.e. separation of
chains, secondary bonds become weaker. As a consequence, the material becomes softer
and more ductile. Swelling is considered as partial dissolution, while the dissolution or
complete solubility is worse than the swelling. Swelling and dissolution effects are
influenced by temperature because of their physiochemical nature.

Bond rupture: Bond rupture in polymers due to degradation is known as scission.

Polymers bonds may get rupture due to many effects like radiation, heat energy, or
chemical reactions. When polymers are exposed to certain types of radiation, which may
result in broken bonds and rearrangement of atoms leads to degradation of polymers. At
elevated temperatures, bonds in polymers may get weakened, leading to deterioration of
polymers. Some chemical elements like oxygen, ozone can alter the chain scission rate as
a result of chemical reactions. This is especially pronounced in vulcanized rubbers.

Weathering: Polymers are exposed to outdoor conditions in many instants of their

service. Any degradation of polymer under these circumstances is termed as weathering,
which in fact is a combination of several different processes. It primarily involves
oxidation, which may be initiated by ultraviolet radiation from the Sun. polymer’s
resistance to weathering to very difficult to quantify and is very diverse.

Some examples of polymer degradation include:

- Deterioration of acrylic paintings and pieces of art

- Decomposition of photographic films

- Decolorization of plastics pieces preserved in museums

Solutions to polymer degradation: As the recognition of polymer degradation improves,

conservation guidelines are beginning to emerge. High-tech solutions which could help in
theory are prohibitively expensive, but tailor made scavengers such as activated charcoal
or Ageless help to create a low oxygen environment. Ageless is a reactive powdered iron
and is normally used to prolong the shelf-life of dry foods by absorbing oxygen.
Epoxidised soya bean oil (ESBO), has also been tested with encouraging results as an
acid absorbing coating on degrading cellulose nitrate.

Want to know how good you are in the subject?

1. Corrosion of metals involves

(a) Physical reactions (b) Chemical reactions (c) Both (d) None

2. The following factors play vital role in corrosion process

(a) Temperature (b) Solute concentration (c) Both (d) None

3. Following equation is related to corrosion rate

(a) Nernst equation (b) Faraday’s equation (c) Either (d) Neither

4. Passivity is due to
(a) Higher EMF (b) Lower EMF (c) Oxide film (d) All

5. Passivity is not reason for inertness of the following

(a) Au (b) Al (c) Ti (d) Ni

6. Difficult to monitor and very dangerous form of corrosion

(a) Galvanic (b) Pitting (c) Crevice (d) Stress

7. This form of corrosion occurs due to concentration difference in a component

(a) Uniform (b) Galvanic (c) Inter-granular (d) Stress

8. Main form of ceramic degradation

(a) Corrosion (b) Weathering (c) Dissolution (d) Swelling

9. The following influences deterioration of polymers

(a) Weather (b) Radiation (c) Temparature (d) All

10. Following is not the main form of polymer deterioration

(a) Corrosion (b) Swelling and Dissolution (c) Weathering (d) Scission

11. When Pt and Co are electrically connected, which one gets corroded

(a) Pt (b) Co (c) None (d) Can’t decide

12. Which of the following can be used for cathodic protection:

(a) Al (b) Cd (c) Cu (d) Either

Answers:

1. b
2. c
3. b
4. c
5. a
6. b
7. c
8. c
9. d
10. a
11. b
12. a