MODULE 3

Corrosion Science and E-waste Management

Introduction

When the metal comes in contact with gaseous or liquid environment they undergo a spontaneous, but
gradual destruction which starts at the surface of metals. Corrosion is the chemical or electrochemical
reaction of a metal with its surroundings. Corrosion is the destructive attack of a material by reaction
with its environment. The serious consequence of the corrosion process has become a problematic issue
to the environment. Worldwide overall cost of corrosion is 3-5 % of gross national product which comes
out to be 276 billion dollar and 2 lakh crore in India annually. It has been estimated that about 20-25 %
of this loss could be saved by the application of corrosion prevention and control. Sudden failure of
material due to corrosion like nuclear reactors, high pressure boilers, chemical plants, petroleum
refineries, oil pipelines, bridges, aeroplanes can have more catastrophic consequences like loss of human
life. It is a fact that about 80-90 % metallic materials produced in the world is disposed off by engineers.
Definition: Gradual deterioration or loss of metal at its surface by chemical or electrochemical reaction
between the metal and the surrounding environment

Electrochemical theory of corrosion

According this theory, corrosion is an electrochemical process and the reactions are similar to galvanic
cell. Oxidation occurs at anode liberating electrons which flow to cathode where reduction occurs. An
aqueous media is required over the surface of metal for the conduction of ions and the completion of
electrochemical circuit between anode and cathode. When a metal like iron is exposed to atmosphere (air
and aqueous media), the following electrochemical changes takes place leading to the corrosion of iron,
a). formation of large number of minute galvanic cells on the surface of metal, b). Large numbers of
minute anodic and cathodic areas are formed on the surface.
Corrosion reactions

Anodic reaction- At the anodic area, oxidation take place, resulting in the corrosion of iron

1. Anode: Fe → Fe2+ +2e-

2. At cathode- It’s depends on corrosion environment

Cathodic reactions

a. Liberation of hydrogen

(i) In Acidic medium- 2H+ +2e- → H2

(ii) In neutral/alkaline medium- 2H2O +2e-→ 2OH- + H2

b. Absorption of oxygen

(i) In Acidic medium- 2H+ + ½ O2 +2e- → H2O

(ii) In neutral/alkaline medium - H2O + ½ O2 +2e- →2OH-

RUST FORMATION

(i) In the presence of excess oxygen

Fe2+ + 2OH- → Fe(OH)2

2Fe(OH)2 + ½O2 + H2O →Fe2O3.3H2O (Reddish brown)

(ii) In the presence of limited oxygen

3Fe(OH)2 + ½O2 →Fe3O4.3H2O (Black colour)

Types of corrosion

According to electrochemical theory, corrosion occurs due to the formation of large number of galvanic
cells on the surface of the metal. A galvanic cell is formed, when there is a difference in potential between
the cathodic and anodic area across the metal surface. It can be happened in different ways.
1. Differential metal corrosion (Galvanic Corrosion)

When two dissimilar metals are in contact with each other, the metal with lower electrode potential
becomes anodic and undergoes corrosion whereas the metal with higher potential becomes cathodic and
remains unaffected. This kind of corrosion is called as differential metal corrosion. The corrosion
depends manly on the difference in potential between two metals. Higher the difference faster is the rate
of corrosion.
When two metals Fe (-0.44 V) and Cu (0.34 V) are in contact: Since Fe has lower reduction potential
compared to Cu, Fe acts as anode and undergoes corrosion whereas Cu acts as cathode and it is protected.
 Anodic oxidation Cathodic reduction

Fe Fe2+ + 2e- ½ O2+2H2O +2e- 4OH-

When two metals Zn (-0.76 V) and Fe (-0.44 V) are in contact: Since Zinc has lower reduction potential
compared to Fe, Znundergoes corrosion and Fe is protected.

Anodic oxidation Cathodic reduction

Zn Zn 2+ + 2e- ½ O2+2H2O +2e- 4OH-

2. Differential aeration corrosion
When a metal is exposed to different concentrations of air (O2), part of the metal exposed to lower
concentration of O2 will have lower potential, and hence becomes anodic and undergoes corrosion. Other
part of the metal exposed to higher concentrations of O2 becomes cathodic and remains unaffected. The
difference of oxygen concentration produces a potential difference and causes corrosion current to flow.
This kind of corrosion is called as differential aeration corrosion.

More
Aerated

Less
Aerated
Example: Fe rod partially immersed in NaCl solution. Part of the metal immersed in solution is exposed
to lower concentration of oxygen becomes anodic area and undergoes corrosion. Part of the metal outside
water is exposed to more oxygen becomes cathodic and remains unaffected.

The reactions may be represented as follows:

At anode : Fe → Fe2+ + 2 e- (Oxidation)
At cathode : 1/2 O2 + H2O + 2 e- →2 OH- (Reduction)
2. (a). Water-line corrosion

It is observed in steel or iron water tanks partially filled with water. Part of the tank just below water
level (water line in contact with water) is exposed to lower concentration of O2, becomes anodic and
undergoes corrosion. Part of the tank above the water line which is exposed to higher concentration
of O2 becomes cathodic and remains unaffected. More intense corrosion is observed just below the
waterline; hence it is called as water line corrosion.

2. (bPittingcorrosion

Pitting corrosion is observed when dust particles or oil drops get deposited over the metal surface.
The portion of the metal covered by dust which is less aerated becomes anodic and undergoes
corrosion. Thus, metal is lost underneath the surface of dust particle forming a deep and narrow
pit. The adjacent area of the metal which is exposed to higher concentration of O2 becomes
cathodic and remains unaffected. Pitting corrosion is a more dangerous, localized form of
corrosion leads the sudden failure of materials.
 Factors affecting rate of corrosion: The rate of corrosion depends on the following factors.

1. Nature of metal: In general the metals with lower electrode potential values are more reactive than
the metal with higher electrode potential values. The rate of corrosion depends upon the difference in
potential between anodic and cathodic area. Higher difference in potential, higher is the corrosion
current flowing and higher will be the rate of corrosion of anodic metal. For example, the active metals
like k, Na, Mg, Zn etc, with low electrode potential values are highly susceptible for corrosion. The
noble metal such as silver, gold, platinum etc, with higher electrode potential values is less susceptible
for corrosion. However, there are few exceptions for this general trend as some metal show the property
of passivitExample: the potential difference between Fe and Cu is 0.78 V which is more than that
between Fe and Sn (0.3 V). Therefore, Fe corrodes faster in contact with Cu than with Sn.

2. Nature of corrosion product: Most of the metals from their oxides as the corrosion product. This
oxide forms a thin film on the surface of the metal and its nature decides the extent of further corrosion.
If the corrosion product is stoichiometric in composition, highly soluble, nonporous with low ionic and
electronic conductivity, then it forms a protective layer over the surface and effectively prevents further
corrosion of metal. Example: Metals which forms protective layer are Al, Cr, Ti, Ta, Mo etc and
corrosion product of metals like Fe, Mg and Zn cannot protect metal from further corrosion.

3. Relative areas of anode and cathode: The rate of corrosion depends on the relative surface area of
anodic and cathodic part. The smaller surface area of anodic part can be smaller, equal or larger the
size of cathodic area. Smaller the size of anodic area and larger the size of cathodic area, then more
intense and faster will be the corrosion occurring at anodic area. When cathodic area is large, demand
for electrons for reduction reaction will be high. To meet this demand, oxidation reaction occurs more
intensely at anodic area. Example: In the coating of Sn on Fe, if some part on Fe is peeled off it results
in smaller anodic area (Fe) and larger cathodic area (Sn). In this case more intense corrosion is observed
at smaller anodic area (Fe).

4. Nature of the environment:

a. pH of the medium: The rate of corrosion increases with decrease in pH. In acidic medium, the rate
of corrosion depends upon the rate of evolution of hydrogen at cathode area. When pH<4 corrosion rate
increases due to higher concentration of H+ ions.

2H+ + 2e- H2

If the pH is between 4 and 10, the rate of corrosion depends upon the availability of O2.

1/2 O2 + H2O + 2 e- → 2 OH-

If the pH > 10 corrosion ceases practically due to formation of insoluble metal hydroxides on the surface
of metal.
 Fe2+ + 2OH- Fe(OH)2

b.Temperature: Generally, rate of the corrosion increases with increase in temperature. As the
temperature increases conductance of the ions in the aqueous medium increases which reduces
the polarization. Therefore, the rate of corrosion increases. Rate of O2 reduction at cathodic area
is doubled for every 30 ºC rise in temperature and also rate of H2 evolution is doubled for every
10 ºC rise in temperature.

c. Conductance of medium: The rate of corrosion increases with increase in the conductance of
the medium. As the conductance of the medium increases, ions can move easily through the
medium. This decreases the polarization potential and due to this the rate of corrosion increases.
For example, metal immersed in sea water (more conducting) corrodes faster than metal immersed
in river water (less conducting).

Corrosion control
According to electrochemical theory, corrosion occurs due to the oxidation and reductions reactions
at the anodic and cathodic areas respectively. These reactions occur simultaneously and are
interdependent. Therefore by decreasing the rate of any of these reactions or by preventing any
one reaction, the rate of corrosion can be decreased. The following methods are commonly used
to control corrosion.
1. Protective coating
a) Anodic Metal Coating: Galvanization
b) Cathodic Metal Coating: Tinning
2. Cathodic protection- Sacrificial Anode Method
3. Anodic protection
4. Corrosion inhibitors
5. Design and selection of materials
 1. Protective coating

Corrosion of metal occurs mainly due to the interaction of metal surface with the O2 and moisture in the
atmosphere. Therefore, corrosion can be prevented by isolating metal from surrounding environment by
coating a protective layer over the surface of the metal.
Anodic Metal Coating- Galvanization: it is the coating of a layer of metal which are anodic to
base metals. Example is Al, Zn etc. in this type of coating, even if base metal is not completely
covered, it will not undergo corrosion. This is due to formation of large anodic area and small
cathodic areas. Example: Coating of Zn or Mg or Cd metal on Fe. It involves the following steps:

1. The iron sheet is passed through solvent to remove grease & oil present on it.
2. The iron sheet is washed with dil. H2SO4 to remove oxide layer (Rust) present on surface (pickling).
3. The sheet is then treated with a mixture of aqueous solution of ZnCl2 and NH4Cl which acts a flux
and then dried.

4. The dried sheet is dipped in molten zinc at 450 ºC.

5. Excess Zinc present on iron sheet is removed by passing through rollers.

Application: Galvanization of iron is carried out to produce roofing sheets, fencing wire, buckets,
bolts, etc.

Anodizing of aluminum: Anodizing is the process of oxidation of outer layer of metal to its metal
oxide by electrolysis. Oxide layer formed over the metal itself acts as a protective layer. In this process
Aluminum is cleaned, degreased polished and taken as anode in an electrolytic cell. It is immersed in
an electrolyte consisting of 5-10% chromic acid. Steel or copper is taken as cathode. Temperature of
the bath is maintained at 35ᵒC. A current density of 100 A /m2 or more is applied which oxidizes outer
layer of Al to Al2O3 that gets deposited over the metal. Sealing is the final step in the anodizing process.
This process is called anodizing of aluminium or anodic oxidation of aluminum.
 Dc Power

Al2O3 H2CrO4

Cathode
Anode

Anodic: 2Al + 3H2O → Al2O3 + 6H+ + 6e-

Cathodic: 6H+ + 6e- → 3H2
Overall : 2Al + 3H2O → 3H2 + Al2O3

Applications: anodized aluminium is used as an attractive highly durable, corrosion resistant

material in roof, buildings, home appliances and computer parts

Cathodic protection:- In cathodic protection, electrons are supplied from the external source to
prevent oxidation of metal at anodic area. Thus anodic area of metal is completely converted to
cathodic area. Since cathodes do not undergo corrosion, the metal is protected against corrosion.
The process where metal to be protected is made cathode, by supplying electrons from an external
source is called as cathodic protection.

There are two methods of cathodic protection

a) Sacrificial anode method

b) Impressed current method
Sacrificial anode method: In sacrificial anode method, the metal to be protected is connected to a more
active metal.For example, when steel pipe is to be protected, it may be connected to a block of Mg or Zn. In
such a situation, Mg or Zn act as anode and provide electrons to the steel pipe. Steel pipe acts as cathode and
is unaffected. Here Mg or Zn which is anode undergoes sacrificial corrosion. When the sacrificial anode gets
exhausted, it is replaced with new ones.
Other examples: Mg bars are fixed to the sides of ships to act as sacrificial anode or Mg blocks are connected
to buried pipe lines.

Electrical conductor

Mg Block
(Anode)
Corrosion penetration rate (CPR)
Corrosion Penetration Rate (CPR) is defined as the speed at which any metal in a specific
environment deteriorates due to a chemical reaction in the metal when it is exposed to a corrosive
environment. The method used to measure the corrosion rate was weight loss method. This method is used
as a measurement of the Corrosion Penetration Rate (CPR) which is expressed in mile per year (mpy) or
millimeter per year (mmpy). CPR can be calculated by the following equation,
Corrosion penetration rate (CPR) = kW/ ρAt
Where, k is a constant, W is the total weight loss, t is the time taken, A is the surface area of the exposed
metal, ρ is the metal density in g / cm. k value depends on unit used, when k = 534 the mpy will be used.
When k = 87.6 mmpy will be used. The CPR is conveniently expressed in terms of either mils (0.001 inch)
per year (mpy) or millimeters per year (mmpy). K=534 for CPR in mpy when surface area of test specimen
is in inch2 and K=87.6 for CPR in mmpy when surface area of test specimen is in cm2 . Here, 1 mil =0.001
inch
Constant CPR in mpy CPR mmpy
K 534 87.6
W (wt loss) mg Mg
ρ g/ cm3 g/ cm3
A inch2 Cm2
t hrs Hrs
 Numerical Problems on CPR

1. A sheet of carbon steel one meter wide by three meters long has lost 40g to corrosion over the past
six months. Convert that mass loss to a penetration rate of the steel in mm units and mpy units. What
could be the corrosion rate? (Carbon steel density=7.8g/ cm3) To calculate CPR in mmpy

Solution: To calculate CPR in mmpy

Given;
K = 87.6
W (wt loss) = 40 g = 40 x 1000 mg
ρ = 7.8 g/ cm3 = 7.8 g/ cm3
A = 1m x 3m = 3m2 = 3x100 x 100 cm2
T = 6 months = 6 x 30 x 24 hrs
We have

K .W
CPR =
 . A.t

87.6 x 40 x1000
CPR =
7.8 x3x100 x100 x6 x30 x 24

CPR = 3.466 x10-3 mmpy

To calculate CPR in mpy

Given;

K = 534

W (wt loss) = 40 g = 40 x 1000 mg

ρ = 7.8 g/ cm3 = 7.8 g/ cm3

A = 1m x 3m = 3m2 = 3 x 1550 inch2

T = 6 months = 6 x 30 x 24 hrs

We have
 K .W
CPR =
 . A.t

534 x 40 x1000
CPR =
7.8 x3x100 x100 x6 x30 x 24

CPR = 0.0503 mpy

2. Calculate the CPR in both mpy and mmpy for a thick steel sheet of area 100 inch2 which experiences
a weight loss of 485g after one year. (Density of steel=7.9g/cm3).

Solution: To calculate CPR in mmpy

Given;

K = 87.6

W (wt loss) = 485 g = 485 x 1000 mg

ρ = 7.9 g/ cm3 = 7.9 g/ cm3

A = 100 inch2 = 100 x 6.45 cm2

t = 1 year = 365 x 24 hrs

1 inch2 = 6.45 cm2

1 cm2 = 0.155 inch2

We have

K .W
CPR =
 . A.t

87.6 x 485 x1000

CPR =
7.9 x100 x6.45 x365 x24

CPR = 0.9518 mmpy

To calculate CPR in mpy

Given;

K = 534

W (wt loss) = 485 g = 485 x 1000 mg

ρ = 7.9 g/ cm3 = 7.9 g/ cm3

A = 100 inch2 = 100 inch2

t = 1 year = 365 x 24 hrs

We have

K .W
CPR =
 . A.t

534 x 485 x1000

CPR =
7.9 x100 x365 x 24

CPR = 37.424 mpy

E-waste management

Introduction: Every year millions of electrical and electronic devices are discarded as products waste and
are thrown away to the environment. These discarded devices are considered as E-waste and crates threat
to the environment and human health. E-Waste management is intended to reduce the adverse effects of
E-waste on human health, the environment, planetary resources, and aesthetics.

Sources of E-waste

1. Consumer electronics: The constant desire for newer devices and gadgets has led to a surge in e-
waste. This includes televisions, computers, mobile phones, and other home appliances.
2. Medical and laboratory equipment: The healthcare and research sectors use a lot of electronic
equipment for diagnostics, treatment, and experimentation.

3. Manufacturing: E-waste can be generated during the manufacturing process.

 4. Entertainment and leisure devices: E-waste can come from entertainment and leisure devices.

5. Network infrastructure upgrades: E-waste can be generated during network infrastructure upgrades.

6. Battery disposal: E-waste can come from battery disposal.

Types of E-Waste

E-Waste has been categorized into following types.

1. Large household appliances: Such as refrigerators and air conditioners

2. Small household appliances: Such as electric toothbrushes, razors, and vaping devices.

3. Information technology (IT) and telecommunications equipment: Such as computers, laptops, printers,
scanners, and photocopiers

4. Consumer electronics: Such as televisions, stereo equipment, and gaming systems.

5. Lighting equipment: Such as LED bulbs.

6. Electrical and electronic tools: Such as tools that are not large-scale stationary industrial tools

7. Toys, leisure, and sports equipment: Such as toys with minor electrical components

8. Medical equipment systems: Such as medical equipment systems like MRI machine, insulin pumps etc.

9. Monitoring and control instruments: Such as monitoring and control instruments

10. Automatic dispensers: Such as automatic dispensers (ATM), Vending machines.

Effects of e-waste on environment

1. Soil contamination
When e-waste is disposed of in landfills, toxic chemicals can leach into the soil and contaminate nearby
crops and water supplies. This can lead to illnesses in humans and animals that consume contaminated
vegetation.

2. Water pollution

When e-waste breaks down, it can release hazardous chemicals into nearby water sources,
contaminating the water and impacting crops, livestock, wildlife, and humans.

3. Air pollution
 Burning e-waste releases harmful pollutants into the air.

4. Direct harm to wildlife

E-waste can have a devastating effect on wildlife, both directly and indirectly.

5. Resource depletion

Technology consumes resources faster than they can be replenished, which can lead to aquifer
depletion, deforestation, mining for fossil fuels, and soil erosion.

Effect on Human health

Effect on Human health

1. Exposure to Harmful Substances

Every year, over 50 million metric tons of e-waste are produced throughout the world.. Workers take
whatever measures possible to get rid of that waste, including burning or recovering valuable materials that
are still useful, like copper and gold. This exposes those people to harmful substances. Many electronics
contain toxic materials like nickel, zinc, lead, chromium, barium and flame retardants. These can all cause
damage to the human body. Lead may get into the blood, kidneys and even the nervous system.

2. Affects Development of Unborn Children

When a pregnant woman is exposed to those harmful substances, it can affect the development and health of
her unborn child both in and out of the womb. Adverse health effects to the child include stillbirth, premature
birth and low birth weight. Further, any exposure the woman has to lead could reduce neonatal behavioral
scores, an increased risk of mental health disorders, behavioral problems and reduced cognitive abilities. It
can also affect a child’s lung function, respiratory system and chronic diseases later in their lives.

3. Air and Water Pollution effects

Another way e-waste affects humans is through air pollution. Often, the electronics that are sent away to
other countries end up in the incinerator. This process releases harmful chemicals and pollutants into the air.
Humans rely on air to breathe, so when that air fills with toxins, it can affect a person’s respiratory system.
The toxins from electronics enter the groundwater, which is what feeds into streams, ponds and lakes.
Humans rely on these freshwater sources, and if they ingest it, it could lead to serious health problems.
 E-waste sources Constituents Health effects
Solder in printed circuit boards, Lead Damage to central and peripheral nervous
glass panels, and gaskets in systems, blood systems, and kidney damage
computer monitors Adverse effects on brain development of
children; causes damage to the circulatory
system and kidney
Chip resistors and semi-conductors Cadmium Toxic irreversible effects on human health
Accumulates in kidney and liver
Causes neural damage
Relays and switches, and printed Mercury Chronic damage to the brain
circuit boards Respiratory and skin disorders due to
bioaccumulation in fishes
Galvanized steel plates and Chromium Causes bronchitis
decorator or hardener for steel
housing
Cabling and computer housing Plastics and Burning produces dioxin that causes
PVC reproductive and developmental problem

Methods of disposal

Non-biodegradable and toxic wastes like radioactive remnants can potentially cause irreparable damage
to the environment and human health if not strategically disposed of. Waste disposal has been a matter
of concern, the main problem growth in population and industrialization. Here are a few methods of
waste disposal. Disposal of E-waste are mainly done in 5 types.
1. Land-filling
2. Incineration
3. Recycling
4. Metal recovery by acid
5. Reuse
1. Secured land-filling: The e-waste is built on the flat land and the pits are pressed into the soil by
putting the e-waste in it. Residues from waste incineration or waste that is not suitable for material
recycling or thermal treatment are deposited in landfills that are compliant with the legal requirements.
If the waste does not fulfil the requirements for landfilling, it must be pre-treated.
 2. Insinuation: In this process the e-waste is lit in a fully closed chamber inside the insulator at a
temperature of 900 to 1000 degree centigrade. Due to which the quantity of e-waste is reduced
considerably and the toxicity of the organic substance present in it is reduced significantly. The smoke
and gas coming out of the chimney in the injector is passed through the Air Pollution Control System
(APCS) and the various types of metals present in the smoke are separated by chemical action and the
gases are treated.

3. Recycling: Devices such as electronic waste, monitors, picture tubes, laptops, keyboards,
telephones, hard drives, CD drives, fax machines, printers, CPUs, modem cables etc. can be recycled.
In this process, various metals and plastics are sabotaged separately and preserved for reuse.
4. Metal recovery by acid: Different types of parts like ferrous and non ferrous metal and printed
circuit board are separated by electronic waste. Different types of metals like lead, copper, aluminum,
silver, gold, platinum etc. are recovered and reused.
5. 5. Reuse: The metals from the old electronic devices can be extracted and reused. Such as from
computers, mobiles, laptops etc

Advantages of Recycling E-Waste

1. Protecting the environment

E-waste recycling prevents the release of toxic chemicals and dust into the air, soil, and
water. These chemicals can contaminate the environment and harm human health.

2. Conserving resources

Recycling e-waste reduces the need to mine for new materials, and instead reuses valuable
resources like metals and plastics to make new products.

3. Creating jobs

E-waste recycling creates jobs for professional recyclers and a second market for recycled
materials.

4. Reducing landfill waste

Landfills can't handle the toxic chemicals in e-waste, so recycling helps to keep them out of landfills

Extraction of Gold from e-waste

Recovering precious metals from e-waste through hydrometallurgical processes is more attractive
economically than other methods. A hydrometallurgical process consists of first a set of operations including
acidic or alkaline dissolution (leaching) of solids. The resulting solutions are then exposed toseparation and
purification methods including deposition, solvent extraction, adsorption, and ion exchange in order to isolate
and concentrate the intended metals.
Step 1: Grinding of the CPUs: First, any dust or other particles were removed from the CPUs. The sizeof
the grind pieces is 1 mm thickness.

Step 2: Leaching in nitric acid: Concentrated nitric acid (65%) is added. Leaching time is 1 h.

Step 3: Leaching in aqua regia: The aqua regia solution is obtained using three volumes of HCl and one
volume of HNO3 (3:1 V/V ratio). Typically, the gold of composite CPU-containing boards is easily
dissolved in 4-to-1 aqua regia. The solution was decanted, and the pieces were subsequently washed with
10 mL of concentrated HCl so that all of the gold content was fed into the solution.

Step 4: Removing the excess nitric acid: Sulfuric acid is added to the solution to accelerate the removal
of nitric acid and sedimentation of the lead as lead sulfate (if present). The time required for thecomplete
removal of nitric acid from this solution is 45 minutes.

Step 5: Precipitation of gold: A certain amount of iron sulfate (per one gram of gold: 4.2 g of iron sulfate)
is dissolved in hot water and gradually added to the gold-containing solution. For better dissolution of
iron sulfate, some drops of HCl can also be used.

Step 6: Washing and Purifying gold deposits: The deposit is dissolved in HCl and boiled. Followed by
boiling, the acid is removed and the deposit is re- washed in HCl to ensure the cleanness of the gold
powder. Eventually, the deposit was filtered and dried at a temperature of 100°C. Sampling and
measuring of precious metals were performed following thefirst and second stages of leaching, after the
stage of gold extraction, and finally following the purification of deposits.