Metals

Metallic Solids

Metallic solids such as crystals of copper, iron, zinc, are composed of metal atoms held together
by metallic bonding. Metallic crystals are primarily body-centered cubic, face-centered cubic,
and hexagonal. In metallic bonding, all of the valence atomic orbitals on all of the atoms in the
metallic solid overlap to give a vast number of molecular orbitals that extend over the entire
solid.

Figure 1. Metallic bonding formed by metallic

solids in group 1 of the periodic table. Muskid,
Wikimedia commons

The large array of overlapping molecular orbitals in the metallic solid is known as the
conduction band and the electrons in this band are said to be delocalized. This metallic solid
structure is often described as a uniform array of metal atoms in a “sea” of delocalized
electrons.

Metallic solids:

1. are good electrical conductors due to the mobility of the delocalized electrons, but
they vary according to their ability to delocalize the valence electrons.
2. are good thermal conductors because the atoms are closely packed together, and the
delocalized electrons can carry kinetic energy through the solid.
3. have high melting points because of the strong attraction between closely packed
positive metal ions and the delocalized electrons. However, the strength of a metallic
bond can vary widely so the energy required to break the bond also varies widely.

Metallic alloys are nonstoichiometric homogeneous mixtures of metals. There are two types
of alloys:

1. Substitutional alloy. Some of the metal atoms in the crystal lattice of the host metal
are replaced by other atoms of the same size. One example of a substitutional alloy is
brass, where one-third of the atoms in a crystal of copper are replaced with zinc atoms.
 2. Interstitial alloy. The atoms of one or more different metals reside in the voids in the
crystal lattice of the host metal. An important example of an interstitial alloy is steel,
where carbon occupies the voids in an iron crystal lattice.

Figure 2. Different atomic mechanisms of alloy formation, showing pure metal, substitutional, and
interstitial structures. (CCO; Hbf878 via https://en.wikipedia.org/wiki/Alloy)

Metalloids

The metalloids that lie on the border between metals and nonmetals in the periodic table exist
as solid crystalline structures with properties between atomic and metallic solids. For example,
silicon and germanium have electrical conductivities much lower than metals, but much higher
than atomic solids such as diamond. These solids are known as semiconductors.

Semiconductors

The intermediate electrical conductivity values of semiconductors are due to the unique
structure of the molecular orbitals in the solid. Both silicon and germanium ( s2p2) have four
valence electrons which occupy four equivalent sp3 hybridized orbitals. These atomic orbitals
overlap with atomic orbitals of other atoms in the crystal to give four molecular orbitals, which
are split into two groups of different closely spaced energies.

Figure 3. The four sp3 hybridized valence atomic orbitals in a silicon atom combine in the silicon crystal
to give molecular orbitals in two closely spaced energy bands: the valence band, which is almost
completely filled at room temperature, and the conduction band, which is almost empty.

The lower energy molecular orbitals are called the valence band where the electrons reside in
traditional covalent bonds between two atoms. The higher energy molecular orbitals form the
conduction band where electrons can become delocalized due to the extended overlap of the
molecular orbitals with surrounding atoms. The energy region between the valence band and
the conduction band is known as the band gap (Eg). Electrons can’t exist in the band gap since
it does not consist of molecular orbitals.

Electrons in the valence band must gain energy equivalent to the band gap in order to reach
the conduction band. Only a few electrons have enough energy to make the transition from the
valence band into the conduction band at room temperature. This small number of electrons in
the conduction band gives silicon and germanium higher electrical conductivities than the
atomic solids, but lower electrical conductivities than the metallic solids.

Doping

There are two ways to increase the conductivity of a semiconductor:

1. Temperature. Increasing the temperature provides kinetic energy, which increases the
number of electrons capable of reaching the conduction band.
2. Doping. Doping is a deliberate introduction of impurities into the crystal structure of a
semiconductor in order to alter the electrical properties of the pure substance.

For the case of silicon, the doping process involves the addition of a group 15 element, such as
arsenic or antimony, which is substituted for the silicon atoms (group 14) in the crystal lattice.
Since group 15 elements (s2p3) have five electrons, this introduces one more electron into the
silicon crystal than is needed for bonding. A semiconductor with this type of doping is called an
n-type semiconductor.

Silicon can also be doped by adding a group 13 element, such as gallium, to the crystal lattice.
This results in one less electron and one unoccupied molecular orbital in the valence band. This
unoccupied molecular orbital is commonly referred to as a hole. As electrons move to fill the
vacant orbitals, they leave behind a silicon atom with a positive charge. A semiconductor of this
type is called a p-type semiconductor.

Figure 4. In an n-type semiconductor, the dopant has an extra electron which can be promoted into the
conduction band, resulting in an increased electrical conductance. In a p-type semiconductor, the dopant
has one less electron than is needed for bonding. The electrons in the valence band will move to occupy
holes when an external voltage is applied, making it appear that the holes are moving in the opposite
direction.
Classification of Engineering Materials

1. Metals and their alloys

a. Ferrous metals – contains iron as their main component ( e.g., cast iron, wrought
iron, and steel)
b. Non-ferrous metals – contains a metal other than iron as their main component
(e.g., copper, aluminum, brass, tin, etc.)
2. Non-metals (e.g., glass, rubber, plastic etc.)

Physical Properties of Metals

The physical properties of the metals include luster, color, size and shape, density, electric and
thermal conductivity, and melting point. The following table shows the important physical
properties of some pure metals:

Metal Density Melting Point Thermal Conductivity

(kg/m3) (°C) (W/m·°C)
Aluminum 2700 660 220
Brass 8450 950 130
Bronze 8730 1040 67
Cast iron 7250 1300 54.5
Copper 8900 1083 393.5
Lead 11400 327 33.5
Nickel 8900 1456 63.2
Silver 10500 960 420
Steel 7850 1510 50.2
Tin 7400 232 67
Tungsten 19300 3410 201
Zinc 7200 419 113
Cobalt 8850 1490 69.2
Molybdenum 10200 2650 13
Vanadium 6000 1750 –
Mechanical Properties of Metals

The mechanical properties of the metals are those which are associated with the ability of
the material to resist mechanical forces and load. The mechanical properties are as
follows:

1. Strength. It is the ability of a material to resist the externally applied forces without
breaking. The internal resistance offered by a part of an externally applied force is called
stress.
2. Stiffness. It is the ability of a material to resist deformation under stress. The modulus
of elasticity is the measure of stiffness.
3. Elasticity. It is the property of a material to regain its original shape after deformation
when the external forces are removed. This property is desirable for materials used in
tools and machines.
4. Plasticity. It is the property of a material which retains the deformation produced
under load permanently. This property of the material is necessary for forgings, for
stamping images on coins and in ornamental work.
5. Ductility. It is the property of a material enabling it to be drawn into wire with the
application of a tensile force. A ductile material must be both strong and plastic.
6. Brittleness. It is the property of a material opposite to ductility. It is the property of
breaking a material with little permanent distortion.
7. Malleability. It is a special case of ductility which permits materials to be rolled or
hammered into thin sheets. A malleable material should be plastic, but it is not essential
to be strong.
8. Toughness. It is the property of a material to resist fracture due to high impact loads
like hammer blows. The toughness of the material decreases when it is heated.
9. Machinability. It is the property of a material which refers to a relative case with which
a material can be cut.
10. Resilience. It is the property of a material to absorb energy and to resist shock and
impact loads. This property is essential for spring materials.
11. Creep. When a part is subjected to constant stress at high temperature for a long
period of time, it will undergo a slow and permanent deformation called creep. This
property is considered in designing internal combustion engines, boilers, and turbines.
12. Fatigue. When a material is subjected to repeated stresses, cracks can initiate and
grow within the material leading to failure, even if the applied stress is below the
material’s ultimate strength. Fatigue failure is considered a type of failure that occurs
due to accumulated damage over time, rather than an instantaneous overload.
13. Hardness. It is a very important property of metals and has a wide variety of
meanings. It embraces many different properties such as resistance to wear, scratching,
deformation, and machinability, etc. The hardness is usually expressed in numbers which
are dependent on the method of making the test.
 The hardness of a metal may be determined by the following tests:
a. Brinell hardness test
b. Rockwell hardness test
c. Vickers hardness test (also called Diamond Pyramid)
d. Shore scleroscope

Ferrous Metals

The principal raw material for all ferrous metals is pig iron which is obtained by smelting ore
with coke and limestone, in the blast furnace. The principal iron ores with their metallic
contents are shown in the following table:

Iron ore Chemical Formula Color Iron content (%)

Magnetite Fe2O3 Black 72
Haemetite Fe3O4 Red 70
Limonite FeCO3 Brown 60-65
Siderite Fe2O3·xH2O Brown 48

Cast Iron

Cast iron is obtained by re-melting pig iron with coke and limestone in a furnace known as
cupola. It is primarily an alloy of iron and carbon. The carbon contents in cast iron varies from
1.7 to 4.5%. It also contains small amounts of silicon, manganese, phosphorus, and sulfur. The
carbon in a cast iron is present as either (a) free carbon or graphite, or (b) combined carbon
or cementite.

Cast iron cannot be used in parts of machines which are subjected to shocks due to its
brittleness. It is, however, still a valuable material due to its low cost, good casting
characteristics, high compressive strength, wear resistance and excellent machinability.

Types of Cast Iron

1. Grey cast iron. It is an ordinary commercial iron composed of 3 to 3.5% carbon, 0.40
to 1.0% manganese, 0.15 to 1.0% phosphorus, 0.02 to 0.15% sulfur, and the rest is
iron. The grey color is due to the fact that carbon is present in the form of free graphite.
It has low tensile strength, high compressive strength, and no ductility. A very good
property of grey cast iron is that the free graphite in its structure acts as a lubricant,
which makes it suitable for those parts where sliding action is desired ( e.g. automotive
cylinder blocks, pipe fittings, agricultural implements, etc.).
2. White cast iron. It shows a white fracture and contains 1.75 to 2.3% carbon, 0.85 to
1.2% silicon, < 0.4% manganese, < 0.2% phosphorus, < 0.12% sulfur and the rest is
iron. The white color is due to the presence of carbon in the form of cementite (also
known as carbide). The white case iron has a high tensile strength and a low
compressive strength. Since it is hard, it cannot be machined with ordinary cutting tools
but requires grinding as a shaping process.
 3. Chilled cast iron. It is a white cast iron produced by quick cooling of molten iron. All
castings are chilled at their outer skin by contact of the molten iron with the cool sand in
the mould.
4. Mottled cast iron. It is a product in between grey and white cast iron in composition,
color, and general properties. It is obtained in castings where certain wearing surfaces
have been chilled.
5. Malleable cast iron. The malleable iron is ductile and may be bent without breaking or
fracturing the section. The tensile strength of the malleable cast iron is usually higher
than that of grey cast iron and has excellent machining qualities.

Alloy Cast Iron

The cast irons discussed above contain small percentages of other components such as silicon,
manganese, sulfur, and phosphorus. These cast irons may be called plain cast irons. The alloy
cast iron is produced by alloying elements like nickel, chromium, molybdenum, copper, and
manganese in sufficient quantities. These alloying elements improve properties such as
strength, wear resistance, corrosion resistance, or heat resistance. Alloy cast irons are
extensively used for gears, pistons, sprockets, pulleys, etc.

Effect of Impurities on Cast Iron

1. Silicon. It may be present in cast iron up to 4%. It provides the formation of free
graphite which makes the iron soft and easily machinable. It also produces sound
castings free from blowholes, because of its high affinity for oxygen.
2. Sulfur. It makes the cast iron hard and brittle. Too much sulfur gives unsound casting,
therefore, it should be kept well below 0.1% for most foundry purposes.
3. Manganese. It makes the cast iron white and hard. It is often kept below 0.75%. It
helps to exert a controlling influence over the harmful effect of sulfur.
4. Phosphorus. It aids fusibility and fluidity in cast iron but induces brittleness. It is rarely
allowed to exceed 1%. Phosphoric irons are useful for casting of intricate design and for
many light engineering castings when cheapness is essential.

Wrought Iron

Wrought iron is the purest iron which contains at least 99.5 to 99.9% iron. The typical
composition of a wrought iron is 0.20% carbon, 0.12% silicon, 0.018% sulfur, 0.02%
phosphorus, 0.070% slag, and the rest is iron. It is a tough, malleable, and ductile material. It
cannot stand sudden and excessive shocks. It can be easily forged or welded. It is used for
chains, crane hooks, railway coupling, water, and steam pipes.

Steel

Steel is an alloy of iron and carbon, with carbon content up to a maximum of 1.5%. Carbon
occurs in the form of iron carbide, and other elements ( e.g., silicon, sulfur, phosphorus, and
manganese) are also present to greater or lesser amount to impart certain desired properties to
it.
Most of the steel produced nowadays is plain carbon steel or simple carbon steel. A carbon
steel is defined as steel which has its properties mainly due to its carbon content and does not
contain more than 0.5% of silicon and 1.5% manganese. The plain carbon steels varying from
0.06% to 1.5% carbon are divided into the following types depending on the carbon content:

1. Dead mild steel – up to 0.15% carbon

2. Low carbon or mild steel - up to 0.15 to 0.45% carbon
3. Medium carbon steel - up to 0.45 to 0.8% carbon
4. High carbon steel - up to 0.8% to 1.5% carbon

Effects of Impurities on Steel

1. Silicon. The amount of silicon in the finished steel usually ranges from 0.05 to 0.30%.
Silicon is added in low carbon steels to prevent them from becoming porous. It removes
the gases and oxides, prevent blow holes and thereby makes the steel tougher and
harder.
2. Sulfur. It occurs in steel either as iron sulfide or manganese sulfide. Iron sulfide,
because of its low melting point produces red shortness, whereas manganese sulfide
does not have such effect. Therefore, manganese sulfide is less objectionable in steel
than iron sulfide.
3. Manganese. It serves as a valuable deoxidizing and purifying agent in steel.
Manganese also combines with sulfur and thereby decreases the harmful effect of this
element remaining in steel. Manganese makes low carbon steels ductile and of good
bending qualities, while it toughens high speed steels and increases its critical
temperature.
4. Phosphorus. It makes the steel brittle. It also produces cold shortness in steel. In low
carbon steels, it raises the yield point and improves the resistance to atmospheric
corrosion. The sum of carbon and phosphorus usually does not excess 0.25%.

Alloy Steel

An alloy steel may be defined as a steel to which elements other than carbon are added in
sufficient amount to produce an improvement in properties. The alloying is done to increase
wearing resistance, corrosion resistance, and to improve electrical and magnetic properties,
which cannot be obtained in plain carbon steels. Following are the effects of alloying elements
on steel:

1. Nickel. It increases the strength and toughness of the steel. Nickel in the range of 2 to
5% contributes great strength and hardness with high elastic limit, good ductility, and
good resistance to corrosion. An alloy containing 25% nickel possesses maximum
toughness and offers the greatest resistance to rusting, corrosion, and burning at high
temperatures. A nickel steel alloy containing 36% nickel is called invar.
2. Chromium. It is used in steels as an alloying element to combine hardness with high
strength and high elastic limit. It also imparts corrosion-resisting properties to steel. The
 most common chrome steel contains from 0.5 to 2% chromium. A nickel chrome steel
containing 3.25% nickel, 1.5% chromium, and 0.25% carbon is used for armor plates.
3. Tungsten. It prohibits grain growth, increases the depth of hardening of quenched
steel and confers the property of remaining hard even when heated to red color. It is
usually used in conjunction with other elements. Steel containing 3 to 18% tungsten is
used for cutting tools.
4. Vanadium. It aids in obtaining a fine grain structure in tool steel. The addition of a very
small amount of vanadium (< 0.2%) produces a marked increase in tensile strength and
elastic limit in low and medium carbon steels without a loss of ductility. The chrome-
vanadium steel containing about 0.5 to 1.5% chromium and 0.15 to 0.3% vanadium
have extremely good tensile strength, elastic limit, endurance limit and ductility.
5. Manganese. It improves the strength of the steel in both the hot rolled and heat-
treated condition. The manganese alloy containing over 1.5% manganese is used
extensively in gears, axles, shafts, and other parts where high strength combined with
fair ductility is required.
6. Silicon. Silicon steel behaves like nickel steel. This steel has a high elastic limit as
compared to ordinary carbon steel.
7. Cobalt. It gives red hardness by retention of hard carbides at high temperatures. It
increases hardness and strength and also residual magnetism and coercive magnetic
force in steel for magnets.
8. Molybdenum. A range of 0.15% to 0.30% molybdenum is generally used with
chromium and manganese to make molybdenum steel. This steel possesses extra tensile
strength and is used for airplane fuselage and automobile parts.

Stainless Steel

Stainless steel is defined as that steel which when correctly heat-treated and finished, resists
oxidation and corrosive attack from most corrosive media. The different types of stainless steel
are:

1. Martensitic stainless steel. The chromium steels containing 12 to 14% chromium

and 0.12 to 0.35% carbon are the first stainless steels developed. These steels are
magnetic and may be hardened by suitable heat treatment and the hardness obtainable
depends on the carbon content.
2. Ferritic stainless steel. The steels containing 16 to 18% chromium and about 0.12%
carbon are called ferritic stainless steels. These steels have better corrosion resistant
properties than martensitic stainless steel but have little capacity for hardening by heat
treatment.
3. Austenitic stainless steel. The steel containing high contents of both chromium and
nickel are called austenitic stainless steel. There are many variations in chemical
composition of these steels, but the most widely used steel contains 18% chromium and
8% nickel with as low carbon content as possible. This steel is non-magnetic and
possesses the greatest resistance to corrosion and good mechanical properties at
elevated temperatures.
Non-ferrous Metals

The non-ferrous metals are usually employed in industry due to the following characteristics:

1. Ease of fabrication (casting, rolling, forging, welding, and machining)

2. Resistance to corrosion
3. Electrical and thermal conductivity
4. Weight

Aluminum

Aluminum is a white metal produced by electrical processes from its oxide (alumina), which is
prepared from a clay material called bauxite. It is a light metal having a specific gravity of 2.7
and melting point of 658 °C. Its good electrical conductivity is an important property and is
widely used for overhead cables. The high resistance to corrosion and its non-toxicity makes it a
useful metal for cooking utensils under ordinary condition and thin foils are used for wrapping
food items.

In its pure state, the metal would be weak and soft for most purposes but becomes hard and
rigid when mixed with small amounts of other alloys. The addition of small quantities of alloying
elements converts the soft and weak metal into hard and strong metal, while still retaining its
light weight.

1. Duralumin. It is an important and interesting wrought alloy. Its composition is 3.5 to

4.5% copper, 0.4 to 0.7% manganese, 0.4 to 0.7% magnesium, and the rest is
aluminum. Due to its high strength and light weight, this alloy may be used in
automobile and aircraft components.
2. Y-alloy. It is also called copper-aluminum alloy. The addition of copper to pure
aluminum increases its strength and machinability. It contains 3.5 to 4.5% copper, 1.2 to
1.7% manganese, 1.8to 2.3% nickel, 0.6% each of silicon, iron, and magnesium, and
the rest is aluminum.
3. Magnalium. It is made by melting the aluminum with 2 to 10% magnesium in a
vacuum and then cooling it in a vacuum or under pressure of 100 to 200 atm. It also
contains about 1.75% copper.
4. Hindalium. It is an alloy of aluminum and magnesium with a small quantity of
chromium.

Copper

Copper is one of the most widely used non-ferrous metals in industry. It is a soft, malleable,
and ductile material with a reddish-brown appearance. Its specific gravity is 8.9 and melting
point is 1083 °C. It is a good conductor of electricity, so it is largely used in making electric
cables and wires for electric machinery and appliances, in electrotyping and electroplating, in
making coins, and household utensils. It is also used for making useful alloys with tin, zinc,
nickel, and aluminum.

1. Copper-zinc alloys (Brass). The most widely used copper-zinc alloy is brass. This is
fundamentally a binary alloy of copper with zinc, each 50%. Addition of 1 to 2% lead
improves the machining quality of brass. It has greater strength than copper but has
lower thermal and electrical conductivity. Brass is very resistant to atmospheric corrosion
and can be easily soldered.
2. Copper-tin alloys (Bronze). The alloys of copper and tin are usually termed bronze.
The useful range of composition is 75 to 95% copper and 5 to 25% tin. The metal is
comparatively hard, resists surface wear and can be shaped or rolled into wires, rods,
and sheets very easily.