Corrosion and Metal Finishing

Module
CORROSION AND METAL FINISHING
2
Syllabus
Corrosion and it’s control: Introduction, Electrochemical theory of corrosion, Factors affecting
the rate of corrosion: ratio of anodic to cathodic areas, nature of corrosion product, nature of
medium – pH, conductivity and temperature. Types of corrosion - Differential metal and
differential aeration (pitting and water line). Corrosion control: Inorganic coating- Anodizing
– Anodizing of aluminum, Cathodic protection - sacrificial anode and impressed current
methods, Metal coatings – Galvanization. Corrosion Penetration Rate (CPR), numerical
problems on CPR.
Metal finishing: Introduction, Technological importance. Electroplating: Introduction,
Electroplating of chromium(hard and decorative). Electroless plating: Introduction, distinction
between electroplating and electroless plating processes. Electroless plating of copper.
Questions and answers
1. Define corrosion. Describe the electrochemical theory of corrosion taking rusting of iron?
Definition: Corrosion is defined as the destruction and consequent loss of metals through chemical
or electrochemical attack by the environment is called corrosion.
Electrochemical theory of reaction: According to electrochemical theory, corrosion takes place
due to the formation of anodic and cathodic sites on the same metal surface or when two different
metals are in contact with each other in a conducting medium.

Oxidation: The anodic reaction is responsible for the dissolution of metal into metal ions.
0
2𝐹𝑒 (𝑠) → 2𝐹𝑒 2+ (𝑎𝑞) + 4𝑒 − 𝐸𝐹𝑒 2+ ⁄𝐹𝑒 = −0.44 𝑉

Cathodic reactions are depending upon the environment. These cathodic reactions are either one
or many as shown below
Corrosion and Metal Finishing

Cathodic Reaction
At the cathode, electrons are absorbed and cause a reduction of constituents. The electrons flow
from the anodic to the cathodic area. At the cathodic area, chemical species present on the surface
of the metal get reduced.
(a) Liberation of Hydrogen: It takes places in the absence of oxygen
(i) In acidic medium: 2H+ + 2e-→ H2↑
(ii) Neutral / alkaline medium
2H2O → 2H++ 2OH-
2H++ 2e- → H2
2 H2O + 2e- → 2 OH- + H2↑
(a) Presence of oxygen: It takes place in the presence of oxygen
(i) Acidic medium: O2+ 4H++ 4e- → 2H2O
(ii) In neutral (or) alkaline medium: O2 + 2 H2O + 4e- → 4 OH-
Fe2+ ions are smaller in size; they diffuse faster than OH- ions and they combine near the cathodic
area forming the insoluble ferrous hydroxide.
2Fe2+ + 4OH-→ 2Fe[OH]2
Ferrous hydroxide
Ferrous hydroxide further combines with oxygen and water resulting in hydrated ferric oxide.
4Fe[OH]2 + O2 + 2H2O →2[Fe2O3.3H2O]
Hydrated ferric oxide
In the presence of limited oxygen ferrous hydroxide is converted into magnetic oxide and it is
known as black rust.
3 Fe[OH]2 + ½ O2 → Fe3O4.3H2O
Magnetic oxide (Black rust)
2. Explain the following factors affecting corrosion:
(a). The ratio of the anode to cathode area
(b).Nature of metals
(c). Nature of corrosion product
(d).pH of medium
(e). Temperature
(f). Conductivity of electrolyte
Corrosion and Metal Finishing

(a) Rate of anodic to cathodic area

 The rate of corrosion is highly influenced by the relative sizes of the anodic and cathodic
areas.
 Two kinds of reaction take place during corrosion, namely, the oxidation reaction is taking
place at the anode and releases the electrons, the reduction reaction is taking place at the
cathode and accepts the electrons.
 The corrosion rate is higher when the anodic area is smaller than the cathodic area.
 If the anodic area is small and the cathodic area is large then all the electrons released by
the anodic area are consumed rapidly at the cathodic area.
 The corrosion rate is lower when the anodic area is larger than the cathodic area.
(b) Nature of metals
 The rate of corrosion is inversely proposal to the standard electrode potential.
1
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑐𝑜𝑟𝑟𝑜𝑠𝑖𝑜𝑛 ∝
𝑆𝑡𝑎𝑛𝑑𝑎𝑟𝑑 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑑𝑒 𝑝𝑜𝑡𝑒𝑛𝑡𝑖𝑎𝑙
 Metals with lower electrode potential are more reactive than the with higher electrode
potentials.
Ex: 1. Active metals toward corrosion: K, Na, Mg, Zn (with low electrode potential
values).
2. Noble metals towards corrosion: Ag, Au, Pt (with high electrode potential values)
(c) Nature of corrosion product
 Most of the metals get converted into thin oxides during corrosion.
 The corrosion product formed on the surface of the metal may (or) may not act as a
protective film.
 If the corrosion product is stoichiometric insoluble non -porous, stable, and uniform that
itself acts as a protective layer on the surface and prevents further corrosion of metal
Example: Al, Cr, Ti, Zr, Mo, Ta, and Ni (forms oxide film)
Example: Fe, Mg, Zn (do not form protective film)
(d) pH of solution
 Hydrogen ion concentration in the media is another important aspect of the corrosion
phenomenon.
 The corrosion rate is higher when pH is less than 3 due to the continuous evolution of
hydrogen at the cathodic region.
 The rate of corrosion is low at pH > 10, in the case of iron, it forms a protective coating
layer of hydroxide of iron.
 At a pH range between 3 to 10, the presence of oxygen is essential for the corrosion of
iron.
Corrosion and Metal Finishing

(e) Temperature
 The rate of corrosion is directly proportional to the temperature. If the temperature is
increased the rate of corrosion also get increases.
Rate of corrosion ∝ Temperature
 An increase in temperature increases the conductance of the corrosion medium, which also
contributes to the increase in corrosion rate.
 In the case of corrosion-resistant passive metals, the rise in temperature decreases the
passive range and thereby increases the corrosion rate.
(f) Conductivity
 The rate of corrosion is directly proportional to the conductivity of the media. The rate of
corrosion increases with an increase in the conductance of the medium.
Rate of corrosion ∝ Conductivity
 The higher the conductivity of the medium, the faster the ions can migrate between the
anodic and cathodic regions of the corrosion cell, in turn, the faster will be the exchange of
electrons at the electrode surface. Therefore, the rate of corrosion is faster in seawater than
the freshwater.
3. Explain the differential metal corrosion?
Differential metal corrosion
 Differential metal corrosion occurs when two different metals are in contact with each other
and are exposed to the corrosive environment.
 The metal with a lower electrode potential value becomes the anode and it undergoes
oxidation and gets corroded.
 The metal with a higher electrode potential value will act as a cathode and remains
unaffected.
Ex: Let us consider a bimetallic sample of iron and copper as shown below.

 The standard electrode potential of Fe is – 0.44 V. The standard electrode potential of Cu

is 0.34 V.
Corrosion and Metal Finishing

 The iron has a lower electrode potential than copper, so it acts as an anode and it undergoes
corrosion.
 copper acts as a cathode and remains unaffected.
The following reactions occur during differential metal corrosion when Fe is in contact with
Cu
At anode: Oxidation: loss of electrons
Fe → Fe2+ + 2e-
At cathode: Reduction: Gain of electrons
2 H+ + 2e- → H2↑
O2+ 2 H2O + 4 e- → 4 OH-
 The rate of galvanic corrosion depends upon factors such as the potential difference
between the anodic and cathodic regions, a ratio of anodic area to cathodic area,
environmental factors, and the tendency of the metal to exhibit passivity, etc.
4. What is differential aeration corrosion and Explain (1) Waterline corrosion (2) Pitting
corrosion?
Differential aeration Corrosion
 It occurs when the metal surface is exposed to differential air (or) oxygen concentration.
 Part of the metal exposed to the lower concentration of oxygen will have lower potential
and therefore act as the anode. This part undergoes corrosion.
At the anode (less O2 concentration): Oxidation
M → M n+ + ne−
 The other part of the metal exposed to the higher concentration of oxygen acts as the
cathode and remains unaffected.
At the cathode (more O2 concentration): Reduction
O2+ 2 H2O + 4 e- → 4 OH-
 The difference in oxygen concentration produces a potential difference and causes
corrosion current to flow from cathode to anode.
Let us consider a strip of Zn immersed partially in a solution of ZnCl2
Corrosion and Metal Finishing

Schematic representation of Differential aeration corrosion

Hence part of the metal inside the water acts as an anode that undergoes corrosion and the part of
the metal above the water level acts as a cathode and remains unaffected. The corrosion product is
formed between anodic and cathodic areas.
Differential aeration corrosion is explained by the below-given examples
Waterline corrosion

Differential aeration corrosion – Waterline corrosion

 This takes place due to the formation of differential oxygen concentration cells.
 The part of metal exposed to the lower concentration of oxygen (dissolved oxygen) acts as
an anodic area.
 The part of the metal above the water level is exposed to the higher concentration of oxygen
acts as cathodic are and remains unaffected.
 A distinct brown line is formed just below the waterline due to the deposition of rust.
 Waterline corrosion is observed usually in steel water tanks and ships floating in seawater
for a long time
Corrosion and Metal Finishing

Pitting corrosion

Differential aeration corrosion – Pitting corrosion

 Pitting corrosion, or pitting, is a form of extremely localized corrosion that leads to the
creation of small holes in the metal. It arises when a small portion of the metallic surface
is covered by dust or scale or oil drops.
 The metal below the dust which is exposed to the lower concentration of oxygen acts as an
anodic area.
 The whole remaining part of the metal which is exposed to the higher concentration of
oxygen acts as a cathodic area and remains unaffected.
 Once a pit is formed corrosion occurs rapidly because of the small anodic area(pit) and
large cathodic area.
5. Explain the process of Anodizing of aluminum and its applications.
Anodizing

 Anodizing is an electrochemical oxidation process for producing a stable aluminum oxide layer
on the surface of aluminum and its alloys.
 Anodizing process is conducted in a wide variety of electrolytes with AC, DC, or a
combination of both.
Components are required to do anodizing
Anode: Polished Aluminium alloys.
Cathode: Steel or copper or lead.
Electrolyte: 5-10 % chromic acid or 10% H2SO4.
Current density: 10-20 mA/cm2
Procedure: Polished aluminum alloy is taken as an anode and immersed in an electrolyte cell
containing 5 – 10 % chromic acid. Inert electrodes like stainless steel or carbon is taken as a
Corrosion and Metal Finishing

cathode. The temperature of the bath is maintained at 35°C. A current density of 10-20 mA/cm2 is
applied to oxidize the outer layer of aluminum to aluminum oxide, which is porous. The pores are
finally sealed by dipping in hot water to produce Al2O3.H2O, which acts as a nonporous protective
layer preventing corrosion.
Electrode reactions
 At anode: (Oxidation): 2Al + 3 H2O → Al2O3 + 6 H++6 e-
 At cathode: (Reduction): 6 H+ + 6 e- → 3 H2
 Overall reaction: 2 Al + 3H2O → Al2O3 + 3H2

Anodizing process

Advantages of the anodizing process

 Increases the corrosion resistance
 Increases in surface hardness and abrasion resistance
 Provides better adhesion for paint primers
 Electrical and thermal insulators
 The porous layer allows for the coloring and sealing of the coating
6. What is Cathodic protection and explain about Sacrificial anodic protection (SAP) and
Impressed cathodic current protection (ICCP) methods
In cathodic protection, electrons are provided from an external source so that the metal or alloy
remains as a cathode.
It is broadly divided into two:
1. Sacrificial anodic protection
2. Impressed current cathodic protection
Corrosion and Metal Finishing

Sacrificial Anode Protection

 In this method, the metal is protected from corrosion by converted into a cathode by
connecting it into a metal that is anodic to it.
 The base metal is usually iron, copper, or brass.
 Metals like Mg, Al, and Zn are more active and hence are used as anodes.
 These metals being more active act as anode undergo corrosion and supply electrons to the
specimen.
 In this way, the protected metals act as cathodes.
 Since anodic metals are sacrificed to protect the metal structure this technique is called the
sacrificial anode method.
Example: Zn or Mg block connected to a buried oil storage tank or pipeline. Pipelines are made
with Fe and its reduction potential is higher than of Mg. So, Mg acts as an anode and protects the
pipelines from corrosion.

Sacrificial Anode Protection method

Advantages
 The method is simple
 Low installation cast
 Minimum maintenance cost
 Does not require powr supply
Disadvantage
 Involves recurring expenditure for replacement of consumed anodes.
Impressed Current Cathodic Protection (Impressed current/Voltage method)
 It is a method of protecting the base metal by application a direct current larger than the
corrosion current, which is called impressed current.
Corrosion and Metal Finishing

 The metal to be protected is made cathode by connecting it to the negative (cathodic)

terminal of a DC source. The positive (anodic) terminal is connected to an inert anode like
graphite.
 The metal structure being cathode does not undergo corrosion. Anode being inert remain
unaffected. Graphite is widely used as the inert anode in this method, Si, Fe can also be
used as the anode.

Impressed current method

7. Explain the process of Galvanizing
Galvanization
1. In this process the base metal is coated with Zinc.
2. Zinc coatings are generally obtained by hot dipping of the base metal in a molten zinc bath and
the process is called galvanization
3. Iron and steel articles are protected from corrosion usually by galvanization because of the low
cost of zinc easy application of the coating and efficient anodic protection afforded.
The Galvanization process involves the following steps.
(i) Degreasing: The steel is immersed in a degreasing bath such as an alkaline caustic
solution to remove organic contaminants such as dirt, oil, and grease from the surface of
the steel. After degreasing the steel is rinsed with water.
(ii) Pickling: Pickling is a pre-passivation process of metal parts with an acid solution,
typically hydrochloric or sulfuric acid, which can remove the oxide scale.
(iii) Fluxing: The metal is treated with a mixture of aqueous solution ZnCl2 and NH4Cl which
acts as a flux. The purpose of the flux is to clean the steel of all oxidation developed and
create a protective coating to prevent any oxidation before entering the galvanizing kettle.
Corrosion and Metal Finishing

After degreasing, pickling, and fluxing, the surface metal is completely free from oxides
and other contaminants that might inhibit the reaction of the iron and molten zinc in the
galvanizing kettle.
(iv) Galvanizing: Once the steel has been completely cleaned, it is ready for immersion in the
zinc bath. The bath temperature ranges from 820-860 F (438-460 C), at which point the
zinc is in a liquid state.
(v) Excess zinc is released by passing the metal through rollers (or) by wiping.
Application:
Galvanized Iron objects are used as ROOFING sheets, Wires, Pipes, Bolt’s, Tubes etc.

Galvanization process
8. What is meant by metal finishing? Mention (any five) technological importance of metal
finishing?
Definition: Metal finishing is a process of modifying the surface of an object to obtain desired
properties.
Metal finishing is essential to develop materials with diverse properties such as corrosion
resistance, good electrical, thermal conductivity, chemical resistance.
Technological importance of metal finishing
• To improve corrosion resistance
• To improve chemical resistance
• To increase abrasion and impact resistance
• To offer the surface thermal (or) optical reflectivity (Mirror)
• To improve electrical or thermal conducting surface
Corrosion and Metal Finishing

• To increase hardness of the surface

• To provide a decorative appearance
• It is used in electrical and electronic components such as capacitors, printed
circuit boards (PCB)
9. Define metal finishing? Explain factors governing electroplating
Definition: Metal finishing is a process of modifying the surface of an object to obtain desired
properties.
The fundamental principle governing metals finishing are
1. Polarization
2. Decomposition potential
3.Over Voltage/Potential
1. Polarization
Defn: Polarization is the change of potential from a stabilized state it is due to the variation of ion
concentration in the electrolyte.
Polarization is an electrode phenomenon. Hence, electrode potential can be determined using
Nernst equation.
0.0591
𝐸 = 𝐸𝑜 + 𝑙𝑜𝑔[𝑀𝑛+ ] 𝑎𝑡 298 𝑘
𝑛
Where Mn+ is the molar concentration of the metal ions surrounding the electrode surface at
equilibrium.
When there is a passage of current the metal ion concentration near the electrode surface decreases
due to the reduction of metal ions.
If the diffusion is slow the electrode potential changes and the electrode is said to be polarized.
The following factors may be responsible for the variation of electrode potential
(a) Distance between the electrodes
(b) Concentration of electrolyte
(c) The temperature of the reaction
(d) Materials used as anode and cathode
2. Decomposition potential
Def: the minimum external voltage that must be applied in order to bring about electrolysis of an
electrolyte.
Corrosion and Metal Finishing

 Decomposition potential (ED) can be determined by the graphical method, ie., current
(I)versus potential (V).
 It can be determined using an electrolytic cell which consists of two platinum electrodes
immersed in a dilute solution of an acid or base.
 When the voltage is varied, at low voltage no reaction occurs and therefore there is a slight
increase in the current.
 On increasing the voltage to slightly above 1.7 V there is an abrupt increase in the current.
The applied voltage of 1.7 V is the ED for dilute acids or bases.

Graphical representation of Decomposition potential

3. Overvoltage (Over Potential)
Definition: It is defined as the excess (or maximum) voltage that must be applied above the
theoretical decomposition potential for continuous electrolysis.

𝑂𝑣𝑒𝑟 𝑣𝑜𝑙𝑡𝑎𝑔𝑒 = 𝐸𝑥𝑝𝑒𝑟𝑖𝑚𝑒𝑛𝑡𝑎𝑙 𝑑𝑒𝑐𝑜𝑚𝑝𝑜𝑠𝑖𝑡𝑖𝑜𝑛 𝑣𝑜𝑙𝑡𝑎𝑔𝑒 − 𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑑𝑒𝑐𝑜𝑚𝑝𝑜𝑠𝑖𝑡𝑖𝑜𝑛 𝑣𝑜𝑙𝑡𝑎𝑔𝑒

Overvoltage depends on several factors like the conductivity of a solution, the nature of electrodes,
etc. It is mainly due to the polarization of electrodes and other side reactions during electroplating
10. What is electroplating? Explain electroplating of chromium (Hard and decorative)
Electroplating
Electroplating is the process by which the coating metal is deposited on the base metal by passing
a direct current through an electrolytic solution, containing the soluble salt of the coating metal.
Corrosion and Metal Finishing

 Decorative chromium coating: Thin coating of chromium with a thickness range of 0.25-
0.75 𝜇m imparts a bright and decorative look to the materials.
 Hard chromium coating: Thick coating of chromium with a thickness range of 2.5-300 𝜇m
impart weak and tear resistance to the materials.

Chromium coating
 Bath composition: 250- 300 g/L of chromic acid and 2.5- 3.0 g/L of con.H2SO4 ( Ratio of
chromic acid to H2SO4 is 100:1)
 pH: 2 – 4
 Temperature: 45-550C
 Current Density: Decorative chromium coating - 145- 430 A /ft2.
Hard chromium coating - 290- 580 A /ft2
 Current efficiency: Decorative chromium coating - 10 - 15 %
Hard chromium coating – 17-21 %
 Agitation: Air agitation
 Anode: Insoluble anode example lead-tin ( Pb – Sn) alloys or lead-antimony (Pb-Sb) alloy
coated with a thin layer of PbO2.
 Cathode: Object to be plated
Substrate/Object pre-treatment: The object is degreased with organic solvent alkali followed
by acid treatment.
Substrate/object post-treatment: After completion of the electroplating process (around 30
minutes), the object has to be kept in a hot air oven maintained at 105- 120 oC for 2 days (48 hrs.)
Then in the furnace at higher temperature (600-8000 C) for 6 to 8hrs.
Corrosion and Metal Finishing

Reactions: Chromium trioxide reacts with water to form chromic acid.

CrO3 + H2O → H2CrO4
Chromic acid is in equilibrium with dichromic acid.
2 H2CrO4 → H2Cr2O7 + H2O
Electrons supplied to the cathode, reduce the salt of chromium to metallic chromium;
Cr2O72- + 14 H+ + 12e- → 2 Cr + 7 H2O
Applications
 Electroplating of chromium is used to protect the metal from corrosion
 On automobiles furnishing, household fittings, and surgical instrument.
 Hard chromium coatings that have high wear resistance are used in ball bearings, cutting
tools, piston rings etc.
 Black chromium coating is used on optical instruments, machine tools, electronic parts.
11. What is electroless plating? Explain electroless plating of copper and applications?
It is the deposition of the metal from its salt solution on a catalytically active surface by a
suitable reducing agent without using electricity.
Example: Electroless plating of copper or nickel etc.
Metal ion + Reducing agent → Metal plated + Oxidized products
Electroless plating of copper
1. Pretreatment and activation of surface
The object (metal/non -metal/alloy) is degreased with organic solvent or alkali followed by acid
treatment. Metals can be directly used along with a suitable reducing agent.
Semiconductors and insulators like plastics, glass quartz, wood thread and other materials need to
be catalytically activated by dipping in SnCl2 containing HCl at 25 ° C followed by palladium
chloride solution (PdCl2). SnCl2 palladium ions on the surface of the object to palladium which
catalyze the deposition reaction.
plating bath composition:
 1.2g /L of copper sulphate (Electro active metal)
 8g/L of formaldehyde (Reducing agent)
 20 g/L of EDTA (Complexing agent and exalting)
 15 g/L of NaOH + 14 g/L of Rochelle’s salt (buffer)
 pH: 11.0
 Temperature :25 oC
Reactions:
Corrosion and Metal Finishing

Cathode (Reduction)
Cu2+ + 2e- → Cu
Anode (Oxidation)
2HCHO + 4OH-→HCOO- + 2H2O + H2 + 2e-
Overall reaction
Cu2+ + 2 HCHO + 4OH- → Cu + 2HCOO- + 2H2O + H2

Electroless plating of copper

Applications
1. Copper plating is printed circuit board (PCB) etc.
12. What are the differences between electroplating and electroless plating?
Difference between Electroplating and Electroless plating
Sl. No. Particular ELECTROPLATING ELETROLESS PLATING

1 Driving force Electrical energy Autocatalytic redox reaction over

a pretreated catalytic surface
2 Anode A separate anode is used Anode reaction takes place on the
which is connected to the surface of the article which is not
terminal of a battery connected to any terminal of
battery Reducing agent→
-
oxidized product + ne
3 Cathode The object is connected to The object is not connected to any
the negative terminal of terminal of a battery
the battery after Mn++ne-→M
Corrosion and Metal Finishing

pretreatment of its surface

cathodic reaction.
4 Reducing agent Reduction is brought about It is treated to make the surface
by electrons. catalytically active; reduction is
brought about by the reducing
agent.

Nature of Pure metal or alloy Metal or alloy with oxidized

5 deposit products as impurities
6 Throwing Good or Poor Better
power
7 Applicability Only to the conductor. Plating of conductor’s
semiconductors and insulators is
easily carried out.

13. Explain the corrosion penetration rate?

The corrosion rate or the rate of material removal as a consequence of the chemical action is an
important corrosion parameter, this may be expressed as the corrosion penetration rate CPR , or
the thickness loss per unit of time , the formula for this calculation is
𝑘×𝑊
CPR =
𝐷×𝐴×𝑇

where k = a constant (K=534 to give CPR in mpy or K=87.6 for CPR in mm/yr)
W = Total weight lost in mg
T = Time taken in hours
A = the surface area of the exposed metal (square inches)
D = the metal density in g/cm³
The CPR can be expressed as: mil per year (mpy) or milimeters per year (mm/yr)

14. A piece of corroded metal alloy plate was found in a submersed ocean vessel ,it was estimated
that the original are plate was 800 cm2 and that approximately 7.6 Kg had corroded a way
during the submersion , assuming a corrosion penetration rate of 4 mm/yr for this alloy in
seawater , estimate the time of submersion in years , the density of alloy is 4.5 g/cm3 .