COLLEGE OF ENGINEERING

Columban College, Inc.

Olongapo City

MIDTERM COVERAGE
(Module 3 & 4)

Chemistry for Engineers

CHE101

Prepared by:

Engr. Jan Alexis B. Monsalud

General Engineering and Applied Sciences

1st Semester
A.Y.2020-2021
Unit 3 - Metals and Corrosion

Learning Module
Chemistry for Engineers

By
Engr. Jan Alexis B. Monsalud

Copyright © 2020, Columban College, Inc.

All rights Reserved

(No part of this module may be reproduced or copied without the permission from the author.)
LESSON 9
CORROSION AND IT’S TYPES

CORROSION

The surface of almost all the metals begin to decay rapidly when exposed to atmospheric
gases, water or other reactive liquid medium. The process of decay metal by environmental
attack is known as corrosion. Metals undergo corrosion and convert to their oxides, hydroxides,
carbonates, sulphides etc. For example, Iron undergoes corrosion to form reddish brown color
rust [Fe2O3⋅nH2O] while Copper undergoes corrosion to form a green film of basic carbonate
[CuCO3 + Cu (OH)2]

CAUSES OF CORROSION
The metals exist in nature in the form of their minerals or ores, in the stable combined forms as
oxides, chlorides, silicates, carbonates, sulphides etc. During the extraction of metals, these
ores are reduced to metallic state by supplying considerable amounts of energy.
Hence the isolated pure metals are regarded as excited states than their corresponding ores.
So, metals have natural tendency to go back to their combined state (minerals/ores).
When metal is exposed to atmospheric gases, moisture, liquids etc., and the metal surface
reacts and forms more thermodynamically stabled compounds.

EFFECTS OF CORROSION
1. Wastage of metal in the form of its compounds.
2. The valuable metallic properties like conductivity, malleability, ductility etc. are lost due
to corrosion.
3. Life span and efficiency of metallic parts of machinery and fabrications is reduced.

TYPES OF CORROSION
There are two main types of corrosion based on the environment:
1. Dry or Chemical Corrosion
2. Wet of Electrochemical Corrosion

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DRY OR CHEMICAL CORROSION

This type of corrosion occurs mainly through the direct chemical action of atmospheric gasses
like O2, halogens, H2S, SO2, N2 or anhydrous inorganic liquid with the metal surface.

TYPES OF CHEMICAL CORROSION

There are three types of chemical corrosion:
1. Oxidation corrosion
2. Corrosion due to other gases
3. Liquid metal corrosion

OXIDATION CORROSION
This is carried out by the direct action of oxygen low or high temperatures on metals in absence
of moisture. Alkali metals and Alkaline earth metals are rapidly oxidized at low temperatures. At
high temperature all metals are oxidized (except Ag, Au, and Pt).
𝑀 → 𝑀 + 2𝑒 (𝑂𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛)
𝑂 + 2𝑒 → 2𝑂 (𝑅𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛)
𝑀 + 𝑂 → 𝑀 + 2𝑂 (𝑀𝑒𝑡𝑎𝑙 𝑂𝑥𝑖𝑑𝑒)

Figure 12 - Oxidation Corrosion

Initially the surface of metal undergoes oxidation and the resulting metal oxide scale forms a
barrier which restricts further oxidation. The extent of corrosion depends upon the nature of
metal oxide.
1. If the metal oxide is stable, it behaves has a protective layer which prevents further
corrosion. E.g., the oxide films of Al, Sn, Pb, Cu, Cr, W etc. are stable and therefore
further corrosion is prohibited.

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 2. If the metal oxide unstable, the oxide layer formed decomposes back into metal and
oxygen. Oxidation corrosion is not possible. E.g., Ag, Au and Pt do not undergo
oxidation corrosion.
3. If the metal oxide layer is volatile, then the oxide layer volatilizes after formation and
leaves the underlying metal surface exposed for further attack. This causes continuous
corrosion which is excessive in molybdenum oxide (MoO 3).
4. If the metal oxide layer is porous, the oxide layer formed has pores or cracks. In this
case the atmospheric oxygen penetrates through the pores or cracks and corrode the
underlying metal surface. This cause continuous corrosion till conversion of metal into its
oxide is completed. Ex: Alkali and alkaline earth metals (Li, Na, K, Mg etc.)

CORROSION DUE TO OTHER GASES

This type of corrosion is due to gases like SO2, CO2, Cl2, H2S, F2 etc. In this corrosion, the
extent of corrosive effect depends mainly on the chemical affinity between the metal and the
gas involved. The degree of attack depends on the formation of protective or non-protective
films on the metal surface which is explained based on Pilling Bedworth rule.
If the volume of the corrosion film formed is more than the underlying metal, it is strongly
adherent; non-porous does not allow the penetration of corrosive gases.
𝐴𝑔 + 𝐶𝑙 → 2𝐴𝑔𝐶𝑙 (𝑝𝑟𝑜𝑡𝑒𝑐𝑡𝑖𝑣𝑒 𝑓𝑖𝑙𝑚)
If the volume of the corrosion film formed is less than the underlying metal, it forms pores/cracks
and allow the penetration of corrosive gases leading to corrosion of the underlying metal. Ex. In
petroleum industry, H2S gas at high temperature reacts with steel forming a FeS scale. Fe(steel)
+ H2S FeS (porous).

LIQUID METAL CORROSION

This corrosion is due to chemical action of flowing liquid metal at high temperatures on solid
metal or alloy. The corrosion reaction involves either dissolution of a solid metal by a liquid
metal or internal penetration of the liquid metal into the solid metal. Ex: Coolant (sodium metal)
leads to corrosion of cadmium in nuclear reactors.

WET CORROSION OR ELECTROCHEMICAL CORROSION

This type of corrosion occurs where a conducting liquid is in contact with the metal. This
corrosion occurs due to the existence of separate anodic and cathodic parts, between which
current flows through the conducting solution.
At anodic area, oxidation reaction occurs there by destroying the anodic metal either by
dissolution or formation of compounds. Hence corrosion always occurs at anodic parts.

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Electrochemical corrosion involves flow of electrons between anode and cathode. The anodic
reaction involves dissolution of metal liberating free electrons.
𝑀→𝑀 + 𝑛𝑒
The cathodic reaction consumes electrons with either evolution of hydrogen or absorption of
oxygen which depends on the nature of corrosive environment.

EVOLUTION OF HYDROGEN
This type of corrosion occurs in acidic medium. For example, considering the metal Fe, anodic
reaction is dissolution of iron as ferrous ions with liberation of electrons.

Figure 13 - Hydrogen Evolution Corrosion

@ Anode:

𝐹𝑒 → 𝐹𝑒 + 2𝑒 (𝑂𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛)

The electrons released flow through the metal from anode to cathode, whereas H+ ions of
acidic solution are eliminated as hydrogen gas.
@ Cathode:
2𝐻 + 2𝑒 → 𝐻 (𝑅𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛)

This type of corrosion causes displacement of hydrogen ions from the solution by metal ions. All
metals above hydrogen in electrochemical series tend to get dissolved in acidic solution with
simultaneous evolution of H2 gas. The anodes are large areas, whereas cathodes are small
areas.

ABSORPTION OF OXYGEN
For example, rusting of iron in neutral aqueous solution of electrolytes in presence of
atmospheric oxygen. Usually the surface of iron is coated with a thin film of iron oxide. If the film
develops cracks, anodic areas are created on the surface. While the metal parts act as
cathodes. It shows that anodes are small areas, while the rest metallic part forms large
cathodes. The released electrons flow from anode to cathode through iron metal.

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@ Anode:

𝐹𝑒 → 𝐹𝑒 + 2𝑒 (𝑂𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛)
@ Cathode:
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𝑂 + 𝐻 𝑂 + 2𝑒 → 2𝑂𝐻 (𝑅𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛)
2
Overall Reaction

𝐹𝑒 + 2𝑂𝐻 → 𝐹𝑒(𝑂𝐻)
If oxygen is in excess, ferrous hydroxide is easily oxidized to ferric hydroxide.
4𝐹𝑒(𝑂𝐻) + 𝑂 + 2𝐻 𝑂 → 4𝐹𝑒(𝑂𝐻)
The product called yellow rust corresponds to 𝐹𝑒 𝑂 ⋅ 3𝐻 𝑂.

Figure 14 - Oxygen Absorption Corrosion

FACTORS INFLUENCING THE RATE OF CORROSION

The factors that affect the rate of corrosion are

1. Nature of metal and its surface
2. Nature of the atmosphere (environment)
3. Nature of the corrosion product

FACTORS BASED ON THE NATURE OF THE METAL

1. The position of the metal in the electrochemical or galvanic series

The type of impurity present in it and its electropositive nature decides the corrosion
of a metal. For example, when iron has impurities like copper, tin, etc. iron corrodes

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 since iron is more electropositive than metals like copper and tin. On the other hand
when iron is coupled with zinc, zinc corrodes since zinc is more electropositive than
iron.
2. Purity of the metal

Generally pure metal does not corrode, as there is no cathode spot available to
induce corrosion.
3. Surface of the metal

A rough surface corrodes readily as it collects more dirt and provides more cathode
spot for corrosion. A polished surface does not corrode easily.
4. Stress corrosion

Stress in a metal surface is produced by mechanical workings such as quenching,

pressing, bending, and riveting improper heat treatment etc. The portion subjected to
more stress acts as anode and other portion act as cathode. This leads to the
formation of stress corrosion. Stress corrosion is noted in fabricated articles of
certain alloys like high zinc brasses and nickel brasses. Caustic embrittlement noted
in boilers is a typical example for stress corrosion, which is due the attack of alkali
present in water on stressed boiler metal.
5. Anode to cathode ratio

When a bigger cathode area covers a smaller anode area, severe corrosion is noted
in the anodes pot. This is called erosion. It is frequently encountered in piping
agitators, condenser tubes etc. where turbulent flow of gases and vapors remove the
coated surfaces resulting in differential cells. Removal of surface coatings can also
be caused by rubbing or striking activities of solids on the coated surfaces.
6. Physical state of the metal

The rate of corrosion is influenced by grain size, orientation of crystals, stress etc.
The smaller the grains size of the metal greater the rate of corrosion.

FACTORS BASED ON THE NATURE OF THE ATMOSPHERE

1. Temperature of the atmosphere (or environment)
The rate of corrosion increases with increase of temperature
2. PH or Acidity
Lower PH -> greater in corrosion.
3. Amount of moisture in the atmosphere
Increase in moisture in the environment increases the rate of corrosion
4. Amount of oxygen

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 In some cases, oxygen enhances the corrosion and in others, it passivates (make metal
passive – prevents corrosion) the metal.
5. Amount of chemical fumes
Industrial fumes like 𝐻𝐶𝐿, 𝐻 𝑆𝑂 produces electrolytes which are acidic in nature and
increases the rate of corrosion.
Examples
1. Buried pipelines and cables passing from one type of soil to another suffers corrosion
due to differential aeration.
2. Lead pip line passing through clay get corroded because it is less aerated than sand.

FACTORS BASED ON THE NATURE OF CORROSION PRODUCT

In some cases, the corroded product sticks to the surface and absorbs more
moisture. This induces further corrosion. Examples:
a. In Rusting of iron, as rust formed over iron absorbs more moisture, rate of rusting of iron
increases.
b. In some cases, the corroded product acts as the protective coating which prevents
further corrosion.
c. Aluminum oxide formed over the surface of aluminum prevents further corrosion and act
as a protective coating. This is the basic principle of Anodization.
d. In some other cases the corroded product falls out of position exposing the fresh metal
surface for further corrosion.
Example: Magnesium Oxide formed over the surface of Magnesium falls out of position
exposing a fresh surface for further corrosion.

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EXERCISES

1. What is corrosion?
2. What is dry corrosion?
3. What is wet corrosion?
4. What type of corrosion takes place in a metal when the anode is small, and the cathode
is large? Why?
5. Research and discuss galvanic cell formation theory.
6. Research and discuss differential aeration theory.
7. What are the factors influencing the rate of corrosion?
8. Explain and give examples of galvanic corrosion.
9. Explain and give examples of differential aeration corrosion.
10. Why corrosion often takes place under metal washers?
11. Welded joints are better that riveted joints in terms of corrosion. Why?

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LESSON 10
CONTROL AND PREVENTION OF CORROSION

Corrosion can be prevented by the following methods:

1. Control of environment
2. Alloying
3. Surface coating
4. Cathodic protection

CONTROL OF ENVIRONMENT

The corrosion rate can be reduced by modifying the environment. The environment can be
modified by the following:
1. Deaeration: Removal of dissolved oxygen and other gases in water by mechanical
agitation is called deaeration. The presence of increased amounts of oxygen is harmful
since it increases the corrosion rate. Deaeration aims at the removal of dissolved
oxygen. Dissolved oxygen can be removed by deaeration or by adding some chemical
substance like 𝑁𝑎 𝑆𝑂 .
2. Dehumidification: Removal of moisture content present in air is called as
dehumidification. This can be achieved by adding silica gel which can absorb moisture
preferentially on its surface.
3. Inhibitors: In this method, some chemical substance known as inhibitors are added to
the corrosive environment in small quantities. These inhibitors substantially reduce the
rate of corrosion.

ALLOYING

Both corrosion resistance and strength of many metals can be improved by alloying.eg.
Stainless steels containing chromium produce a coherent oxide film which protects the steel
from further attack.

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SURFACE COATING

Corrosion of metal surfaces is a common phenomenon. To protect a metal surface from

corrosion, the contact between the metal and the corrosive environment (air, moisture. corrosive
gases, etc.) is to be cut off. This is done by coating the surface of the metal with a continuous,
non-porous material. Such a coating is referred to as surface coating or protective coating. In
addition to protective action, such coatings also give a decorative effect and reduces wear and
tear.
Objectives of Coating Surfaces
1. To prevent corrosion
2. To enhance wear and scratch resistance
3. To increase hardness
4. To insulate electrically
5. To insulate thermally

METAL COATING
Surfacing coatings made up of metals are known as metallic coatings. These coatings separate
the base metal from the corrosive environment and also function as an effective barrier for the
protection of base metals. The metal which is coated upon is known as the base metal. The
metal applied as coating is referred to as coat metal.
The different methods used for metal coating are.
1. Hot-Dipping

In the process of hot dipping, the metal to be coated is dipped in the molten bath of
the coating metal. Such hot dip coatings are generally nonuniform. The common
examples of hot dip coatings are galvanizing and tinning.
a. Galvanization
The process of coating a layer of zinc over iron is called galvanization. The steel
article is first pickled with dilute sulphuric acid to remove traces of rust, dust, etc.
at 60-90OC for about 15 -20 minutes. Then this metal is dipped in a molten zinc
bath maintained at 430 OC.
When zinc is coated over iron, zinc, and iron forms a galvanic cell. The
electropositive zinc forms the anode and undergoes corrosion. Hence iron is
protected from corrosion by sacrificial protection method.
The surface of the bath is covered with ammonium chloride flux to prevent oxide
formation on the surface of molten zinc. The coated base metal is then passed
through rollers to correct the thickness of the film.

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 It is used to protect roofing sheets, wires, pipes, tanks, nails, screws, etc.
b. Tinning
The coating of tin over iron is called tin plating or tinning.
Tinning is done to protect iron, steel and copper from corrosion. It is also called
tinplating. Since tin is non-toxic, it is mainly used in food industry for coating food
containers. Tin-coated utensils are used for storing foodstuffs, pickles, oils, etc.
Tin is nobler metal (more cathodic) than iron. It is more resistant to atmospheric
corrosion. Thus, uniform layer of tin protects iron from corrosion.
Tinning the base metal is first pickled with dilute sulphuric acid to remove surface
impurities. Then it is passed through molten tin covered with zinc chloride flux.
The tin coated article is passed through a series of rollers immersed in a palm oil
bath to remove the excess tin. Galvanizing is preferred to tinning because tin is
Cathodic to iron, whereas zinc is anodic to iron. So, if the protective layer of the
tin coating has any cracks, iron will corrode. If the protective layer of the zinc
coating has any cracks, iron being Cathodic and is not corroded. The corrosion
products fill up the cracks, thus preventing corrosion.

2. Metal spraying
3. Cladding
4. Cementation
a. Sherardizing – Cementation with Zinc powder.
b. Chromizing - Cementation with 55% Chromium powder & 45% Alumina is called
Chromizing.
c. Calorizing – Cementation with Aluminum and Alumina powder is called
Calorizing
5. Electroplating or electrodeposition.

Electroplating is process in which the coat metal is deposited on the base metal by
passing a direct current through an electrolytic solution by means of electrolysis.

ELECTROPLATING PROCESS

In electroplating, the cleaned base metal is made as the cathode and the coat metal is taken as
the anode. A solution of the coat metal salt is taken as the electrolyte. The electrodes are
connected to the battery and DC current is passed. Now electrolysis takes place and the coat
metal is deposited over the base metal.

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The nature of coating depends on 1) the current density 2) time 3) temperature and 4) the
concentration of the electrolyte.
For example, to electroplate a spoon made of copper with silver, the copper spoon is taken as
the cathode. A silver plate is taken as the anode. Silver thiocyanate solution is the electrolyte.
When the electrodes are connected to a DC source of electricity, silver is deposited over the
copper spoon.

The following electrolytes are used for coating other metals:

1. Copper sulphate – Copper
2. Nickel sulphate – Nickel
3. Chromic acid - Chromium

FACTORS AFFECTING ELECTROPLATING

1. Cleaning of the article is essential for a strong adherent electroplating.
2. Concentration of the electrolyte is a major factor in electroplating.
3. Low concentration of metal ions will produce uniform coherent metal deposition.
4. Thickness of the deposit should be minimized in order to get a strong adherent coating.
5. Additives such as glue and boric acid should be added to the electrolytic bath to get a
strong adherent and smooth coating.
6. The electrolyte selected should be highly soluble and should not undergo any chemical
reaction.
7. The pH of the electrolytic bath must be properly maintained to get the deposition
effectively.

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ANODE AND CATHODE PROTECTION

ANODIZING
Anodizing is the process of coating aluminum oxide on the surface of aluminum or its alloy.

This type of coating is produced on non ferrous metals like Al, Zn, Mg and their alloys, by anodic
oxidation process, by passing direct electric current though a bath in which the metal is
suspended from anode. Here the base metal behaves as an anode. For anodizing 8% sulphuric
acid is used as the electrolyte. Since it is a good oxidizing agent, it oxides aluminum (at the
anode) into aluminum oxide. The electrolytes are sulphuric, chromic, phosphoric, oxalic or boric
acid.
Anodized coatings have more corrosion resistance due to thicker coating
Aluminum oxide coatings are formed by the oxidation taking place on the aluminum surface at
moderate temperatures (35 to 40 OC) and moderate current densities. The formed oxide film is
initially thin and gain thickness by the continuous oxidation of aluminum anode. The surface of
oxide film contains pores, which may cause corrosion. The pores can be sealed by exposing to
boiling water then the oxide is converted into monohydrate (𝐴𝑙 𝑂 ⋅ 𝐻 𝑂). This process is called
sealing process.
The anodized aluminum and its alloy are used in:1.aircrafts 2.window frames 3.machine parts
4.fancy article and 5.Refrigerator, etc.

CATHODIC PROTECTION
The principle involved in cathodic protection is to force the metal behave like a cathode. Since
there will not be any anodic area on the metal, corrosion does not occur. There are two types of
cathodic protection.
1. Sacrificial anodic protection

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 In this technique, a more active metal is connected to the metal structure to be
protected so that all the corrosion is concentrated at the more active metal and thus
saving the metal structure from corrosion. This method is used for the protection of
sea going vessels such as ships and boats. Sheets of zinc or magnesium are hung
around the hull of the ship. Zinc and magnesium being anodic to iron get corroded.
Since they are sacrificed in the process of saving iron (anode), they are called
sacrificial anodes. The corroded sacrificial anode is replaced by a fresh one, when
consumed completely.
Important applications of sacrificial anodic protection are as follows:
a. Protection from soil corrosion of underground cables and pipelines.
b. Magnesium sheets are inserted into domestic water boilers to prevent the
formation of rust.
2. Impressed current cathodic protection

In this method, an impresses current is applied in an opposite direction to nullify the

corrosion current and converting the corroding metal from anode to cathode. This
can be accomplished by applying enough direct current from a battery to an anode
buried in the soil and connected to the corroding metal structure which is to be
protected.

The anode is in a backfill (composed of gypsum) so as to increase the electrical contact

with the soil. Since in this method current from an external source is impressed on the
system, this is called impressed current method
This type of protection is given in the case of buried structures such as tanks and
pipelines.

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EXERCISES

1. What is Galvanization?
2. What is anoding?
3. What is base metal?
4. What is coat metal?
5. Galvanizing is preferred to tinning. Why?
6. What is Sherardizing?

7. What is a sacrificial anode? How does it function?

8. Differentiate between galvanizing and tinning.
9. What is anodizing? How it is carried out? what are its applications?
10. What is tinning? What are its merits & demerits?

11. Explain the various methods of prevention of corrosion.

12. Explain briefly about cathodic protection.
13. Explain briefly about electroplating.

14. Why is moderate current density employed during electroplating?

15. Chromium anode is not used in chromium plating. Give Reason.

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LESSON 11
ORGANIC COATINGS

Organic coating includes paints and varnishes. In this lesson, we are going to study about paint
and its components. A little introduction to special paints used is also discussed. Further we are
going to study about varnish its types and their preparation.

PAINTS

Paint is a dispersion of pigment in drying oil.

Paint coating is given to both metallic and wooden articles to protect them from corrosion and to
give better surface appearance. Paint covers the manufacturing defects in the articles.
When paint is applied to a metal surface, the thinner evaporates while the drying oil slowly
oxidizes forming of pigmented film.
Components of paints and their functions
The important constituents of paint are as follows.
1. Pigments
2. Vehicle or drying oils or medium
3. Thinners
4. Driers
5. Fillers or extenders
6. Plasticizers
7. Anti-skinning agents

PIGMENTS
A pigment is a solid and color-producing substance which gives desired color to the paint.
Examples
a. White Pigments – Titanium oxide, Zinc oxide
b. Black pigments – Graphite, carbon black
c. Red pigments – Red lead, Indian red (𝐹𝑒 𝑂 )

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Functions
The following are the functions of pigments:
1. A pigment gives opacity and color
2. It covers manufacturing defects
3. A pigment gives strength to the film
4. Protects by reflecting destructive ultraviolet rays

VEHICLE OR DRYING OILS OR MEDIUM.

The liquid portion in which the pigment is dispersed is called a medium or vehicle.
Examples
Linseed oil, dehydrated castor oil, soybean oil and fish oil.
Functions
1. Vehicles hold the pigment particles together on the metal surface.
2. They form the protective film by evaporation or by oxidation and polymerization of the
unsaturated constituents of the oil.
3. Vehicles give better adhesion to the metal surface.
4. They impart water repellency, durability, and toughness to the film.

THINNER
Thinners are added to paints to reduce the viscosity of the paints in order to make it easy to
apply on the metal surface.
Examples
Turpentine, kerosene, and petroleum spirit
Functions
1. Thinners reduce the viscosity of the paint to render it easy to handle and apply to the
metal surface.
2. They dissolve the oil, pigments etc. and produce a homogeneous mixture.
3. Thinners evaporate rapidly and help the drying of the film.
4. They increase the elasticity of the film.

DRIERS
Driers are used to speed up the drying process and accelerate the drying of the oil film by
oxidation, polymerization, and condensation.

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Examples
Naphthenates and resins of lead, cobalt, and manganese.
Function
Driers act as oxygen carrier catalysts which help the absorption of oxygen and catalyze the
drying of the oil film by oxidation, polymerization and condensation.

FILLERS OR EXTENDERS
Fillers are used to increase the volume of the paint and to reduce the cost. It increases the
durability of the paint.
Examples
Asbestos, talc, china clay, calcium sulphate and calcium carbonate.
Functions
1. Fillers serve to fill the voids in the film.
2. They reduce the cracking of the paints.
3. Fillers increase the durability of the paints.
4. They reduce the cost of the paint.

PLASTICIZERS
Plasticizers are chemicals added to increase elasticity of the film and to prevent cracking of the
film.
Examples
Tertiary amyl alcohol, triphenyl phosphate, triglyceryl phosphate.

ANTI-SKINNING AGENTS
They are chemicals added to the paint to prevent skinning of the paint.
Examples
Polyhydroxy phenols, guaiacol, etc.

VARNISHES

Varnish is a homogenous colloidal dispersion of natural or synthetic resin in oil or spirit medium.
If the medium is oil it is known as oil varnishes.

18
If the medium is spirit it is known as spirit varnishes.
It is used as a protective and decorative coating to the wooden surfaces. It provides a hard,
transparent, glossy appearance and durable film to the coated surface.
There are two main types of varnishes:
1. Oil Varnish
2. Spirit Varnish

OIL VARNISH.
Oil varnishes are more difficult to manufacture. Resins that are used in the preparation of oil
varnishes are high molecular weight substances and are not easily soluble in oil. The resin is
taken in an aluminum vessel and heated over a fire pit or in a small furnace. When resin melts ,
the temperature is slowly increased to about 300 OC. This process is known as gum running.
Some cracking or depolymerization of the resin takes place and about 25 per cent of the resin is
lost in the form of fumes.
The required quantity (about 25 per cent of the weight of the resin) of boiled oil or linseed oil
along with driers is separately heated to 200 to 220 OC and is slowly added to the heated resin
with constant stirring until thorough combination has taken place. This operation is known as
cooking. Overheating must be avoided as it causes discoloration of the varnish.
The kettle is removed from the furnace and allowed to cool, white spirit is then added (which is a
petroleum fraction, boiling between 150 OC and 200 OC). It is the most common thinner. The
varnish is stored in tanks for some days for maturing. Foreign matter and particles of resin,
which have not dissolved, settle during this period. During maturing, the color of the varnish also
improves, and it becomes more homogenous. The varnish is filtered and packed for marketing.

SPIRIT VARNISH
A Spirit varnish is a dispersion of resin in spirit.
The resin and spirit are placed in a cylindrical drum. plasticizer and other components are
added. The resin is dissolved by agitating the mixture or by rotating the drum. It is then filtered
and used. The final product is called spirit varnish.

DIFFERENCE BETWEEN PAINT AND VARNISH

Paint Varnish
1 Paint has pigment There is no pigment in the
varnish
2 It can be applied to both It can be applied only to the
metals and wooden articles wooden articles
3 It is opaque It is transparent

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SPECIAL PAINTS

In addition to the normal ingredients some special chemicals are in corporated to paints for
some specific purposes. They are commonly known as special paints.

LUMINOUS PAINTS
Luminous paints are visible in the dark. Since it contains luminophore pigments (like 𝐶𝑑𝑆, 𝑍𝑛𝑆)
that are used for visibility in the dark .They absorb light radiations and emit them in the dark.
The active components in luminous paint are specially prepared phosphorescent materials like
𝐶𝑑𝑆, 𝑍𝑛𝑆, etc. For color effect in luminous paints, certain chemicals like copper salts (green),
silver salts (blue), cerium and uranium salts (yellow), etc. are added
They find application in inks, advertising signboards, road marks, road traffic signs, number
plates of vehicles, watch dials, map, chart, etc.

FIRE-RETARDANT PAINTS
The paints which retard the fire are called as fire-retardant. This paint contains the chemicals
PVC, Chlorinated rubber, urea formaldehyde and carbonate pigments which are fire-resistant in
nature. These substances at higher temperatures breakdown to give the noninflammable gases
like CO2,NH3,HCl and HBr. These gases are noncombustible and do not support combustion.
Mainly used in defense, industrial, commercial, education and residential complexes The most
frequent source of a fire in any hotel, restaurant or residence. The walls, doors and even kitchen
counters should be protected against the spread of fire.
False ceiling, Lift, Equipment Rooms, Aircraft Safe deposit vaults, lockers, Computer Server
rooms, Power plants Chemical Plants, Storage Tanks, structures in Sugar Mills, Textile Mills
and Floorings.
Aluminum Paint
The base material in aluminum paint is a fine powder of aluminum. The ground fine powder of
aluminum is suspended in either spirit varnish or an oil-varnish depending on the requirement.
When paints are applied, the thinner evaporates and oil, if any, undergoes oxidation and
polymerization. A bright adhering film of aluminum is obtained on the painted surface.
Wooden and metallic article for interior and exterior decoration.
Advantages of aluminum paint:
1. It possesses a good covering power.
2. It imparts very attractive appearance to the surface.
3. It has fairly good heat-resistance.
4. It has very good electrical resistance
5. The painted film is waterproof.

20
 6. The electrical surface is visible even darkness.
7. Corrosion protection for iron and steel surface is better than all other paints.

DISTEMPERS
Distempers are water paints. They contain chalk powder, glue and pigment dissolved in water.
They are very cheap and can be easily applied on walls. They are durable and give pleasing
finish to walls. The ingredients of distemper are
1. Whiting agent or chalk powder (the base)
2. Glue or casein (the binder)
3. Coloring pigment and
4. Water (the solvent or thinner).
Advantages
1. Distempers are cheaper than paints and varnishes
2. They can be applied easily on plasters and wall surfaces in the interior ofthe buildings.
3. They are durable.
4. They give smooth and pleasing finish to walls.

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EXERCISES

1. Define paint.
2. What is Varnish?
3. What is distemper?

4. Write a short note on luminous paints.

5. Write a note on Aluminum paints.
6. Explain about Fire retardant paint.
7. What are the differences between paint and varnish?

8. What are the components present in the paint? Explain their functions.
9. How is oil varnish preferred?
10. Explain briefly about special paints.

11. What are toners?

22
Unit 4 – Chemistry of Materials

Learning Module
Chemistry for Engineers

By
Engr. Jan Alexis B. Monsalud

Copyright © 2020, Columban College, Inc.

All rights Reserved

(No part of this module may be reproduced or copied without the permission from the author.)
LESSON 12
CEMENT

Cement is a building material. It is applied in the form of a soft paste with sand and water and
later its sets into a hard mass. It is a mixture of calcareous material and argillaceous material. It
is a mixture of silicates of calcium and aluminum.

PORTLAND CEMENT

A paste of cement with water on setting and hardening gave a hard mass whose color and
hardness were similar to those of stones from Portland in England. Thus, it derived the name
Portland cement. Portland cement is a mixture of silicates of calcium and aluminum.

MAJOR CONSTITUENTS OF CEMENT

1. Dicalcium silicates(2𝐶𝑎𝑂 ⋅ 𝑆𝑖𝑂 )-28%[𝐶𝑎 𝑆]
2. Tricalcium silicates(3𝐶𝑎𝑂 ⋅ 𝑆𝑖𝑂 )-46%[𝐶 𝑆]
3. Tricalcium aluminates(3𝐶𝑎𝑂 ⋅ 𝐴𝑙 𝑂 )-10%[𝐶𝑎 𝐴]
4. Tetra calcium aluminoferrite(4𝐶𝑎𝑂 ⋅ 𝐴𝑙 𝑂 ⋅ 𝐹𝑒 𝑂 )-9%[𝐶𝑎 𝐴𝑙𝐹𝑒]
5. Small quantities of 𝐶𝑎𝑂 and 𝑀𝑔𝑂-7%

MANUFACTURE OF CEMENT BY WET PROCESS

RAW MATERIALS REQUIRED

1. Calcareous materials – These materials supply lime
2. Examples: Limestone, chalk, marble
3. Argillaceous materials – These materials supply silica
4. Example: Clay
3. Powdered coal (fuel)
4. Gypsum

1
PROCESS
1. The limestone is crushed and powdered well.
2. The clay is intimately mixed with water in wash mill.
3. The powdered limestone and wet clay are mixed and made into a paste in a grinding
mill. This paste is known as slurry. The slurry contains 30 to 40% water.
4. The slurry is fed into the top of the rotary kiln. The rotary kiln is made of steel plates lined
with fire bricks.
5. The kiln is heated by burning powdered coal which is injected at the lower end by an air
blast.
6. In the upper part of the kiln (drying zone) where the temperature is 400°C, the slurry
loses all its water.
7. When the charge enters the middle portion of the kiln (calcinations zone) where the
temperature is about 900 – 1000°C, limestone decomposes to form 𝐶𝑎𝑂 and 𝐶𝑂 .
8. Then the charge enters lower portion of the kiln (burning zone) where the temperature is
about 1400°C. Lime and clay combines to form calcium silicates and aluminates called
clinker.
9. The hot clinker is cooled and then grinded with 3 – 4% gypsum in a grinding mill.
Gypsum retards the setting of cement. In the absence of gypsum, cement sets rapidly.
10. The cement coming out of the grinding mills is stored in concrete storage tanks and then
packed in bags.

SETTING OF CEMENT

When water is added to cement, sudden setting of cement occurs (flash set). The hardening of
cement by the addition of water is known as setting of cement.

2
The setting and hardening of cement are mainly due to hydration and hydrolysis reactions of the
different constituents present in cement. The dicalcium silicate (𝐶𝑎 𝑆), tricalcium silicate (𝐶𝑎 𝑆),
tricalcium aluminate (𝐶𝑎 𝐴𝑙) and tetracalcium aluminoferrite (𝐶𝑎 𝐴𝑙𝐹𝑒) present in cement
undergoes hydration.
2𝐶𝑎 𝑆 + 4𝐻 𝑂 → 𝐶𝑎 𝑆 ⋅ 3𝐻 𝑂 + 𝐶𝑎(𝑂𝐻) + 𝐻𝑒𝑎𝑡 58.6 𝑘𝐽
2𝐶𝑎 𝑆 + 6𝐻 𝑂 → 𝐶𝑎 𝑆 ⋅ 3𝐻 𝑂 + 3𝐶𝑎(𝑂𝐻) + 𝐻𝑒𝑎𝑡 76.3 𝑘𝐽
𝐶𝑎 𝐴𝑙 + 6𝐻 𝑂 → 𝐶𝑎 𝐴𝑙 ⋅ 6𝐻 𝑂
𝐶𝑎 𝐴𝑙𝐹𝑒 + 7𝐻 𝑂 → 𝐶𝑎 𝐴𝑙 ⋅ 6𝐻 𝑂 + 𝐶𝑎𝐹𝑒 ⋅ 𝐻 𝑂
During this process, anhydrous soluble compounds are converted into hydrated insoluble
compounds. The hydrated insoluble gel hardens due to dehydration. Finally, after dehydration,
the insoluble gel sets into hard mass. It surrounds the sand and binds it strongly with
interlocking crystals of 𝐶𝑎(𝑂𝐻) . This process is known as setting of cement.

EXERCISES

1. What is cement?
2. What is Portland cement?
3. Why is gypsum added during the manufacture of cement?

4. What are the raw materials required for the manufacture of Portland cement?
5. Write a note on setting of cement.

6. Explain the manufacture of Portland cement by wet process.

7. What are the various types of cement?

8. How the quality of cement is tested?

3
LESSON 13
CERAMICS

Ceramics find wide application in engineering, medical and domestic usage. Ceramics are
increasingly used in motor parts (e.g. ceramic disc brakes, ceramic balls, etc.). Ceramic engine
does not require cooling system. They withstand heat up to 3300°C. One of the main
applications of ceramics is white pottery.

CERAMICS

Ceramics are inorganic non-metallic materials that are processed at high temperature and
subsequent cooling.
Examples: Ceramic wash basin, ceramic tiles, etc.

WHITE POTTERY

They are ceramic materials of china clay which is in white color after firing is called white wares.
They consist of a refractory body and glossy coating.
The raw materials used for manufacture of white pottery are given below.
1. China clay(kaolin)[𝐴𝑙(𝑂𝐻) 𝑆𝑖𝑂 ]
2. Feldspar [𝐾𝐴𝑙𝑆𝑖𝑂 ]
3. Flint (𝑆𝑖𝑂 )/quartz.

MANUFACTURE OF WHITE POTTERY

1. Preparation of Body Ware
The raw materials are made into fine powder and mixed with water to form a paste. The
excess of water is removed by filtration. The article is prepared from the paste either by
hand molding or by using potter’s wheel. It is dried and then fired in a ‘biscuit’ oven to
get porous ware called ‘Bisque’.
2. Glazing
In order to make the porous ware (Bisque) into water-tight article, it is covered with glaze
by melting it over the surface of the body. Slurry of glaze is prepared by mixing Feldspar,

4
 silica and boric oxide with water. Now the fired articles are dipped in the slurry of glaze
and again fired. Now a smooth, glossy and non-porous surface is formed on the articles.
3. Decoration
To decorate the article, design is made on the article using pigments and fired again. For
example: Iron oxide pigments red color, Cobalt oxides give blue color.

USES OF WHITE WARE

They are used for the preparation of
1. Spark plugs
2. Electrical insulators
3. Laboratory equipment
4. Crucibles, dishes, insulators sanitary wares etc.

GLAZING

Glazing is the process of giving a smooth, glossy, non-porous surface on the articles using
glazes. A glaze is a fine powder consisting of glass forming materials like lead silicates,
borosilicates etc. They are colorless glazing and color glazing mixtures. Colorless glazing is
done with glass forming materials like lead silicate and borosilicate. Color glazing is done by
mixing colored metal pigments with glass forming materials.
Example:
1. Iron oxide for red and brown
2. Copper oxide for green
3. Cobalt oxide for blue

PURPOSE OF GLAZING
1. To get decorative effect.
2. To make the surface impervious (non-porous) to liquids and water.
3. To improve appearance of the article.
4. To increase the durability of ceramic material.
5. To get a smooth glossy appearance.
6. To protect the surface from atmospheric action.

5
METHODS OF GLAZING
1. Salt Glazing
In salt glazing, common salt (sodium chloride) is used for getting glossy films over
articles. The process consists of throwing sodium chloride into furnace when the article
is in red-hot condition. At high temperature, sodium chloride vapors react with silica in
the article to form a smooth glossy and impervious film of ‘sodium silicate’. This is known
as salt glazing.
2. Liquid Glazing

Slurry of glaze is prepared by mixing Feldspar, silica and boric oxide with water. Now
the articles are dipped into the slurry of glaze and then fired. Now a smooth, glossy,
and non-porous surface is formed on the articles. This is known as Liquid Glazing.

EXERCISES

1. What are ceramics?

2. Define white pottery.
3. What is called bisque?
4. What is glazing?

5. What are the raw materials required for the manufacture white pottery?
6. List the uses of white pottery.
7. Explain salt glazing.

8. Describe the manufacture of white pottery.

9. What are the purposes of glazing?
10. Write a note on glazing.

11. What are the engineering applications of ceramics?

6
LESSON 14
LUBRICANTS

Whenever a machine works, its moving, sliding or rolling parts rub against each other with the
result of that a friction is developed. This friction causes a lot of wear and tear of the concerned
surfaces. Further due to friction, large amount of energy is dissipated in the form of heat and
thus causes loss in the efficiency of a machine. Moreover, the heat produced due to friction
causes damage to the moving parts.
The above ill effects can be minimized by applying a thin layer of certain substances known as
lubricant in between the moving parts.
The process of applying the lubricant in between the two moving or sliding surfaces is called as
lubrication.
Lubricant may be defined as the substance which reduces the friction between the two moving
surfaces or parts of a machine.

CHARACTERISTICS OF LUBRICANTS

1. It should have enough viscosity and oiliness.

2. It should have flash and fire points higher than the operating temperature of the
machine.
3. It should be chemically inert.
4. It should not come out of the surface under pressure.
5. It should not evaporate easily.
6. It should stick on the surface.
7. It should leave low carbon residue.
8. It should not form emulsion with water.
9. It should have cloud and pour points lower than the operating temperature of the
machine.
10. The volatility of the lubricating oil should be low.
11. It should possess a higher resistance towards oxidation and corrosion.

7
CLASSIFICATION OF LUBRICANTS

Lubricants may be broadly classified as follows.

1. Solid lubricants
2. Semi-solid lubricants
3. Liquid lubricants

SOLID LUBRICANTS

The most widely used solid lubricants are graphite and molybdenum sulphide.
Solid lubricants are used in the following areas.

a. For heavy machinery working as a crude job at very high loads.

b. When the operating temperature or load is very high.
c. Where a liquid or semi-solid lubricant film cannot be maintained.

GRAPHITE
Graphite is an allotrope of carbon. Graphite has a layered structure of carbon atoms. The
carbon atoms are joined together by strong covalent bonds. The adjacent layers are held
together by the weak Vanderwall’s force. Thus, they form a network of hexagons. Graphite is
soapy to touch, noninflammable and not oxidized in air below 375°C.It is used as a lubricant in
the form of powder or as suspension in oil or water. It fills the cavities and prevents the friction.
It is used for lubricating the joints or railways tracks.
Graphite can be used as a dry powder or as a colloidal dispersion. A dispersion of graphite in
water is called aquadag and that in oil is called oildag.
It is used as a lubricant in IC engines, air compressors, lathes, foodstuff industry, railway track
joints, general machine job works, etc.

MOLYBDENUM SULPHIDE
Fine powder of molybdenum sulphide is used as lubricant. It has the capacity to withstand very
high temperature. It is stable in air upto 500°C.
It is used as lubricant in high-speed machines.

8
SEMI-SOLID LUBRICANT

GREASE
It is a mixture of mineral oil and soap. It is used for heavy load and low speed machines. It is
mainly used in bearing and gears. Grease is a semisolid lubricant obtained by thickening of
lubricating oil by the addition of a metallic soap. The thickener is usually sodium, calcium, and
lithium or aluminum soap.
Greases are manufactured by saponification of fats with alkali followed by adding hot lubricant
oil under severe agitation. Their properties depend on both the base used for saponification and
the fatty acid present in the oil.

LIQUID LUBRICANTS

VEGETABLE OILS
They are commonly used liquid lubricants.
Examples: Castor oil, coconut oil, etc.
They are classified as drying and semi-drying oils. They are easily oxidized by atmosphere.

ANIMAL OILS
They are oils of animal origin. They are mainly animal fats.
Examples: Tallow oil, whale oil, lards oil, coconut oil and olive oil etc.
They are very costly. Hence, they find little use as lubricants. They are also easily oxidized by
atmosphere.

MINERAL OIL
Hydrocarbons with higher molecular mass obtained by the fractional distillation of petroleum are
used as lubricants. They are obtained from the paraffin residue.
Examples: Paraffin oil, lubricating oil, etc.

BLENDED OILS
They are mixture of vegetable oils and petroleum products. They show improved properties.
Different oils are suitably mixed depending on the requirement. They are synthetic lubricants.

9
EXERCISES

1. What is a lubricant?
2. How are lubricants classified?
3. Mention the uses of graphite.
4. Mention the uses of molybdenum sulphide.

5. How are lubricants classified? Give examples.

6. Write a note on semi-solid lubricant.

7. List the essential characteristics of lubricants.

8. Write a note on solid lubricants.
9. Write a note on liquid lubricants.

10. What types of lubricants are used for transformers?

11. Why does graphite act as a good lubricant on the surface of the motion?

10
LESSON 15
ADHESIVES

Any substance capable of holding materials together by surface attachment is known as

adhesive.
The bodies held together by an adhesive are known as ‘adherends’, while the process of
holding one adherend to another by adhesive is called ‘bonding’. The final assembly of two
adherends and the adhesive is called ‘bond’.
The quality of an adhesive is judged by the following factors.
1. Degree of tackiness (i.e., stickiness)
2. Rapidity of bonding
3. Strength of bond after setting or drying and
4. Durability
Examples: Starch, glue, gum, phenol-formaldehyde, cellulous nitrate, PVC, etc.

REQUIREMENTS OF A GOOD ADHESIVE

1. It should have high tackiness.

2. It should form a strong bond.
3. It should have low viscosity.
4. The bonding should be rapid.
5. It should be highly durable.
6. It should have negligible creep under stress.
7. It should be water repellant.
8. It should be resistant to insects and fungi.

CLASSIFICATION OF ADHESIVES
Adhesives are classified into two types.
a. Natural adhesives
b. Synthetic adhesives

11
NATURAL ADHESIVES

STARCH
Starch adhesives are obtained by heating a starch suspension in water at 150 oC. The
characteristics of starch adhesives are,
1. They are very cheap.
2. They spread quickly and dry quickly.
3. They do not give any foul smell.
4. They can be applied in cold as well as hot conditions.
5. They have low resistance to moisture and low adhesive strength.
They are used in making envelopes, stamps, notebooks, binding books, etc.

SHELLAC
Shellac is one the oldest adhesive. It has to be applied in hot condition. The bond developed
has good strength, good hardness, and low thermal conductivity.
It is used for making belts, conveyer belts, etc.

ASPHALT
It is the residue obtained during the fractional distillation of petroleum.
Uses
1. It is used for water-proofing of roofs.
2. It is used for road making.

SYNTHETIC ADHESIVES

THERMOPLASTIC SYNTHETIC RESINS

Thermoplastic synthetic resins form soluble, fusible and poor water resistance adhesives. They
get softened on heating.
Examples: Cellulose nitrate, PVC, etc.
1. Cellulose Nitrate

12
 Cellulose nitrate is used as a raw material for solvent adhesives. Cellulose nitrate
mixed with alcohol is well known as ‘collodion’. The adhesive film developed by
cellulose nitrate is tough. But the adhesive film is inflammable and affected by strong
acids and strong alkalis.
It is used in cloth and foot-wear industry.
2. PVC (Polyvinyl Chloride)

PVC forms hard adhesive films, resistant to atmospheric conditions and chemicals.
It is used for bonding metals, glass, etc.
It is used in sealing of food materials.

THERMOSETTING SYNTHETIC RESINS

Thermosetting synthetic resins have good adhesive properties by forming a network of
three-dimensional cross-linked structures. The bonding obtained is moisture resistant, heat
resistant and fungi proof.
Examples: Phenol-formaldehyde resins, urea-formaldehyde resins, etc.
1. Phenol-Formaldehyde Resin
This is pressure sensitive type of adhesive. The adherend surfaces after being
coated with this adhesive are subjected to curing by heat and pressure. It is
available as solid or liquid form. The bonded film obtained is hard, highly resistant to
the action of water, fungi, insects, etc.
Uses
a. It is used for making water-proof plywood, laminates, etc.
b. It is used for bonding articles in aircraft and ship building.
c. It is used for bonding wood and metal.
d. It is used for bonding plywood and wooden surfaces.
2. Urea-Formaldehyde Resin
It is a transparent, syrupy compound used in the form of aqueous solution or spray
dried powders. The addition of water to this resin helps in forming continuous film
with cross linkages and rapid setting properties. The bonded film obtained is
resistant to temperature, moisture, etc. It deteriorates by the action of acids and
alkalis. It has the same use as phenol-formaldehyde resin.

13
EXERCISES

1. Define adhesive.
2. Name two natural adhesives.
3. Name two synthetic adhesives.
4. Mention the uses of shellac.
5. Mention the uses of asphalt.
6. Mention the uses of cellulose nitrate.
7. Mention the uses of PVC.
8. Mention the uses of phenol-formaldehyde.
9. How are adhesives classified? Give examples.
10. Write a note on shellac.
11. Write a note on starch..
12. Write a note on cellulose nitrate.
13. Write a note on PVC.
14. Write a note on phenol-formaldehyde.
15. Write a note on urea-formaldehyde.
16. What are the requirements of a good adhesive?
17. Write a note on the following natural adhesives.
a. Shellac
b. Starch
c. Asphalt
18. Write a note on the following synthetic adhesives
a. Cellulose nitrate
b. PVC
c. Phenol-formaldehyde
d. Urea-formaldehyde
19. Explain the ways by which adhesives develop strength.

14