Metals

SCI 401 LECTURE 8

Occurrence of Metals
Ore - a mineral deposit concentrated enough to allow economical
recovery of a desired metal
Occurrence of Metals
► Some pure metals – native metals example - gold (not reactive)
► Most metals obtain from oxides example - iron oxide or from
carbonates or sulfides converted to oxides
► Sodium and potassium are isolated primarily from brines
(solutions of NaCl and KCl). Potassium was the first alkali metal to
be prepared by electrolysis.
► Lithium is obtained mostly from the mineral spodumene,
LiAl(SiO3)2.
 Occurrence of Metals
►  
Metallurgy
► Metallurgy is the science and technology of separating
metals from their ores and of compounding alloys.
► An alloy is a solid solution either of two or more metals,
or of a metal or metals with one or more nonmetals.
► The three principal steps in the recovery of a metal from
its ore:
(1) preparation of the ore,
(2) production of the metal, and
(3) purification of the metal.
Preparation of the Ore

► Removal of impurities, a.k.a gangue which are usually clay and silicate
minerals.
► Methods:
❑ Flotation
❑ Electromagnetism (ex.: magnetite and Cobalt)
❑ Amalgamation (ex. Gold and Silver)
Production of Metals

► The production of a free metal is a reduction process.

► Preliminary operations may be necessary to convert the ore to
a chemical state more suitable for reduction.
CaCO3(s) 🡪 CaO(s) + CO2(g)
2PbS(s) + 3O2(g) 🡪 2PbO(s) + 2SO2(g)

► Most major metallurgical processes now in use involve

pyrometallurgy, procedures carried out at high temperatures.
Production of Metals
Chemical Reduction
► We can use a more electropositive metal as a reducing agent to
separate a less electropositive metal from its compound at high
temperatures:
V2O5(s) + 5Ca(l) 🡪 2V(l) + 5CaO(s)
TiCl4(g) + 2Mg(l) 🡪 Ti(s) + 2MgCl2(l)
Cr2O3(s) + 2Al(s) 🡪 2Cr(l) + Al2O3(s)
3Mn3O4(s) + 8Al(s) 🡪 9Mn(l) + 4Al2O3(s)
► In some cases, even molecular hydrogen can be used as a reducing
agent, as in the preparation of tungsten (used as fi laments in light
bulbs from tungsten (VI) oxide:
WO3(s) + 3H2(g) 🡪W(s) + 3H2O(g)
Production of Metals
Electrolytic Reduction
► Electrolytic reduction is suitable for very electropositive metals, such
as sodium, magnesium, and aluminum. The process is usually carried
out on the anhydrous molten oxide or halide of the metal:
2MO(l) 🡪 2M (at cathode) + O2 (at anode)
2MCl(l) 🡪 2M (at cathode) + Cl2 (at anode)
The Metallurgy of Iron
Raw Materials
► Iron Ore 🡪 Iron ores contain from 50% to around 70% iron, depending
on grade (hematite is almost 70% iron).
Ores used in the production of iron:
❑ hematite (Fe2O3)
❑ magnetite (Fe3O4)
❑ siderite (FeCO3)
❑ limonite (Fe2O3-xH2O, where x is typically around 1.5).
► Scrap iron and steel are also widely used today as raw materials in
iron- and steel making.
The Metallurgy of Iron
Raw Materials
► Coke 🡪 Supplies heat for chemical reactions and produces carbon
monoxide (CO) to reduce iron ore
► Limestone 🡪 Used as a flux to react with and remove impurities in
molten iron
► Hot gases (CO, H2, CO2, H2O, N2, O2, and fuels) 🡪 Used to burn coke
The Metallurgy of Iron
►Chemical reactions:
Using hematite as the starting ore: 3Fe2O3 + CO 🡪 2 Fe3O4 + CO2
Fe3O4 + CO 🡪 3FeO + CO2
FeO + CO 🡪Fe + CO2
CO2 reacts with coke to form more CO: CO2 + C (coke) 🡪 2CO
Final reduction of FeO to iron: FeO + CO 🡪 Fe + CO2

► A mixture of calcium silicate and calcium aluminate that remains

molten at the furnace temperature is known as slag.
The Metallurgy of Iron
Removal of Impurities:
CaCO3(s) 🡪CaO(s) + CO2(g)
CaO(s) + SiO2(s) 🡪 CaSiO3
CaO(s) + Al2O3(s) 🡪 Ca(AlO2)2(l)
The Metallurgy of Iron
►Blast Furnace Process
– a refractory-lined chamber with a diameter of about 9 to 11 m (30
to 35 ft) at its widest and a height of 40 m (125 ft).

Pig iron – product of blast furnace

⮚ contains over 4% C, plus other impurities: 0.3-1.3% Si, 0.5-2.0% Mn,
0.1-1.0% P, and 0.02-0.08% S.
 To produce iron, a
charge of ore, coke, and
limestone are dropped
into the top of a blast
furnace. Hot gases are
forced into the lower
part of the chamber at
high rates to accomplish
combustion and
reduction of the iron.
Steel
Steel 🡪 an alloy of iron containing from 0.02% and 2.11% carbon by weight. It often
includes other alloying elements: manganese, chromium, nickel, and molybdenum

Steels produced by BOF or electric furnace are solidified for subsequent processing
either as cast ingots or by continuous casting.
❑ Casting of ingots –a discrete production process
Molds made of high carbon iron, tapered at top or bottom for removal of
solid casting. The mold is placed on a platform called a stool. After
solidification the mold is lifted, leaving the casting on the stool. 10-12 hr may
be required for casting to solidify.
❑ Continuous casting –a semi-continuous process
Continuous casting is widely applied in aluminum and copper production,
but its most noteworthy application is in steel-making. Dramatic productivity
increases over ingot casting. Continuous casting reduces solidification time by
an order of magnitude. Steel is poured into tundish and flows into a water-
cooled continuous mold; it solidifies as it travels down in mold
Steel Making

► A furnace called a cupola is commonly used for converting

pig iron into gray cast iron.
CaO(s) + SiO2(s) 🡪 CaSiO3
P4O10(l) + 6CaO(s) 🡪 2Ca3(PO4)2(l)
MnO(s) + SiO2(s) 🡪 MnSiO3(l)
 Steel Making
► Basic oxygen furnace (BOF)
• Accounts for 70% of steel production in U.S
• Adaptation of the Bessemer converter
• Bessemer process used air blown up through the
molten pig iron to burn off impurities
• BOF uses pure oxygen
• Typical BOF vessel is 5 m (16 ft) inside diameter
and can process 150 to 200 tons per heat
• Entire cycle time (tap-to-tap time) takes 45 min
 Steel Making
► Basic oxygen furnace (BOF)
The composition and uses of various types of steel.

Type Composition (% by mass) Uses

C Mn P S Si Ni Cr Others
Sheet products,
Plain 1.35 1.65 0.04 0.05 0.06 - - Cu(0.2- 0.6)
tools
High Construction,
0.25 1.65 0.04 0.05 0.15-0.9 0.4-1.0 0.3-1.3 Cu(.01-.08)
Strength steam turbines
Kitchen utensils,
Stainless 0.03-1.2 1.0-10 .04-.06 .03 1-3 1-22 4.0-27 -
razor blades
Four Categories of Steel

1. Plain carbon steels - Carbon is the principal alloying element, with only
small amounts of other elements (about 0.5% manganese is normal).
Strength of plain carbon steels increases with carbon content, but ductility
is reduced.

a) Low carbon steels - contain less than 0.20% C, used in automobile

sheet-metal parts, plate steel for fabrication, railroad rails
b) Medium carbon steels - range between 0.20% and 0.50% C, used in
machinery components and engine parts such as crankshafts and
connecting rods
c) High carbon steels - contain carbon in amounts greater than 0.50%,
used in springs, cutting tools and blades, wear-resistant parts
Four Categories of Steel

2. Low alloy steels

⮚ Iron-carbon alloys that contain additional alloying elements in
amounts totaling less than 5% wt.
⮚ Mechanical properties superior to plain carbon steels for given
applications due to higher strength, hardness, hot hardness, wear
resistance, toughness, and more desirable combinations of these
properties
⮚ Heat treatment is often required to achieve these improved
properties
Four Categories of Steel
3. Stainless steels
► Highly alloyed steels (typically with Cr and/or Ni) designed for corrosion
resistance.
► In addition to corrosion resistance, stainless steels are noted for their
combination of strength and ductility.
► While desirable in many applications, these properties generally make SS
difficult to work in manufacturing.
► Significantly more expensive than plain C or low alloy steels since chromium
carbide forms to reduce available free Cr.
Several additional high alloy steels have been developed and are also classified as
stainless steels:
❑ Precipitation hardening stainless – typical composition = 17% Cr and 7%Ni, with additional
small amounts of alloying elements such as Al, Cu, Ti, and Mo.
❑ Duplex stainless - mixture of austenite and ferrite in roughly equal amounts
Four Categories of Steel
4. Tool steels – is a class of (usually) highly alloyed steels designed for use as
industrial cutting tools, dies, and molds. To perform in these applications,
they must possess high strength, hardness, hot hardness, wear resistance, and
toughness under impact. Tool steels are heat treated.
Purification of Metals
► Distillation – fractional distillation for metals with low boiling points like Hg, Mg, Zn.
❑ Mond process (Ludwig Mond)- fractional distillation of Ni.
Carbon monoxide gas is passed over the impure nickel metal at about 70°𝐶 to
form the volatile tetracarbonylnickel (𝑏. 𝑝. 43°𝐶), a highly toxic substance, which
is separated from the less volatile impurities by distillation:
𝑁𝑖(𝑠) + 4𝐶𝑂(𝑔) → 𝑁𝑖(𝐶𝑂)4(𝑔)
Pure metallic nickel is recovered from 𝑁𝑖(𝐶𝑂)$ by heating the gas at 200°𝐶:
𝑁𝑖(𝐶𝑂) 4(𝑔) →→ 𝑁𝑖(𝑠) + 4𝐶𝑂(𝑔)
► Electrolysis
Purification of Metals
► Zone refining
A metal rod containing a few impurities is drawn through an electrical heating
coil that melts the metal (Figure 4). Most impurities dissolve in the molten metal. As
the metal rod emerges from the heating coil, it cools and the pure metal crystallizes,
leaving the impurities in the molten metal portion that is still in the heating coil. When
the molten zone carrying the impurities, now at increased concentration, reaches the
end of the rod, it is allowed to cool and is then cut off.
BAND THEORY OF ELECTRICAL CONDUCTIVITY

► states that delocalized electrons move freely through “bands” formed by

overlapping molecular orbitals.

In a metallic crystal, the atoms are packed closely together, so the energy levels
of each atom are affected by the immediate neighbors of the atom as a result of orbital
overlaps. The interaction between two atomic orbitals leads to the formation of a
bonding and an antibonding molecular orbital.
Because the number of atoms in even a small piece of magnesium is enormously
large (on the order of 1020 atoms), the number of molecular orbitals they form is also
very large. These molecular orbitals are so closely spaced on the energy scale that they
are more appropriately described as a “band” (Figure 5). The closely spaced filled
energy levels make up the valence band. The upper half of the energy levels
corresponds to the empty, delocalized molecular orbitals formed by the overlap of the
3p orbitals. This set of closely spaced empty levels is called the conduction band.
Semiconductors
► are normally not conductors, but will conduct electricity at elevated temperatures
or when combined with a small amount of certain other elements (examples are
silicon and germanium from Group 4A elements).
► Examples: Transistors and solar cells
If the energy needed to excite electrons from the valence band into the conduction
band is provided, the solid becomes a conductor. Note that this behavior is opposite
that of the metals. A metal’s ability to conduct electricity decreases with increasing
temperature because the enhanced vibration of atoms at higher temperatures tends to
disrupt the flow of electrons.
Enhancement of semiconductor’s ability to conduct electricity can be done, this is
by means of adding small amount of certain impurities to the element, this process is
called doping. Impurities of this type are known as donor impurities, because they
provide conduction electrons. Solids containing donor impurities are called n-type
semiconductors, where n stands for negative (the charge of the “extra” electron).
Physical Properties of Metals
► Shiny appearance. Metals show a metallic luster. Due to their shiny appearance
they can be used in jewelry and decorations. Particularly gold and silver are widely
used for jewelry. In the old days, mirrors were made of shiny metals like silver.
Silver is a very good reflector. It reflects about 90% of the light falling on it. All
modern mirrors contain a thin coating of metals.
► Hardness. Metals are mostly harder to cut. Their hardness varies from one metal to
another. Some metals like sodium, potassium and magnesium are easy to cut.
► Malleability. Metals can be hammered into thin sheets. Most metals are malleable.
Gold and Silver metals are the most malleable metals. They can be hammered into
very fine sheets. Thin aluminium foils are widely used for safe wrapping of
medicines, chocolates and food material.
► Ductility. Metals can be drawn into thin wires. Wires are made from copper,
aluminium, iron and magnesium.
► Electrical conductivity. Electric wires in our homes are made of aluminium and
copper. They are good conductor of electricity. Electricity flows most easily
through gold, silver, copper and aluminium. Gold and silver are used for electrical
contacts in computers. Copper wires are used in electrical appliances while
aluminium is generally used for making electrical cables.
Physical Properties of Metals
► Thermal conductivity. Metals are good conductors of heat. Cooking utensils
and water boilers are also made of iron, copper and aluminium, because they
are good conductors of heat.
► Sonorous. Metals make a ringing sound when struck. Therefore, they are used
for making bells. Metal wires are used in musical instruments.
► Toughness. Metals have high capacity to absorb energy better than any other
classes of materials. Metals such as iron are very strong. Therefore, it is
widely used in the construction of buildings, bridges, railway lines, carriages,
vehicles and machinery.
► High melting point. All metals except mercury have high melting points.
Therefore, they retain their form and shapes under normal conditions.
► Elasticity. Metals can be stretched to some degree without breaking. Metals
like tungsten have high tensile strength.
► Magnetism. Some metals are magnetic and some are not.
► No two metals are absolutely identical. For example,
 Iron is magnetic and copper is not.
 Gold and Platinum are malleable and ductile but do not react with water.
 Sodium is highly reactive and reacts vigorously with water to form a solution
of sodium hydroxide.
Chemical Properties of Metals
► When metals are burned with the presence of oxygen, they combine with
oxygen to form metallic oxides.
Metal + Oxygen (from air) 🡪 Metal Oxide
► Water reactivity. Different metals react differently with water. Sodium reacts
violently with water forming sodium hydroxide and hydrogen. Magnesium
reacts mildly with water but vigorously with steam. Zinc and iron react mildly
with steam. Copper, gold and silver do not react with water at all. Most
metals, on reacting with water produce hydroxide.
► Acid reactivity. Most metals react with acids to produce salts and hydrogen.
► Metal displacement reactions. Metals displace other metals in a metallic
compound when they have higher reactivity.
 Arrangement of Metal Reactivity in
Decreasing Order
Li K Na Ca Mg Al Mn Zn Cr Fe Ni SN Pb H Cu Bi Sb Hg Ag Pt Au
Displace Hydrogen from Acids                

Displace Hydrogen from Steam                      

Displace Hydrogen                                  
on cold water
Corrosion
Corrosion is the deterioration of metals by an electrochemical process like
rusting of iron and tarnishing of silver.
2Fe(s) + O2(g) + 4H+(aq) 🡪 2Fe2+(aq) + 2H2O(l)
4Fe2+(aq) + O2(g) + (4+2x)H2O(l) 🡪 2Fe2O3·xH2O(s) + 8H+(aq)
⮚ Copper forms a layer of copper carbonate (CuCO3), a greenish substance
called platina
⮚ Silver forms silver sulfide (Ag2S) 
Corrosion Protection
► Passivation – the surface of the iron metal is made inactive by treating it with
a strong oxidizing agent such as nitric acid to form a thin oxide layer at the
surface. Sodium chromate is used for radiators and cooling systems.
► Alloys – combining the metal with other metals to reduce its tendency to
oxidize.
► Plating- applying a thin layer of other metals like tin or zinc on the surface of
the iron.
► Cathodic protection - a process in which metal that is to be protected from
corrosion is made the cathode in what amounts to a galvanic cell.
Designation Schemes for Steels
► Designation Scheme for Steels - developed by American Iron and Steel
Institute (AISI) and Society of Automotive Engineers (SAE), so designation
often expressed as AISI or SAE
► Specified by a 4-digit number system YYXX, the first two numbers YY
represent the alloying elements and the last two numbers XX represent the
carbon % in hundredths of percentage points
Designation Schemes for Steels

► Stainless Steels – three-digit AISI numbering scheme; First digit indicates

general type, and last two digits give specific grade within type
Non-ferrous Metals

► Nonferrous Metals – metal elements and alloys not based on iron

► Most important engineering metals in nonferrous group are aluminum, copper,
magnesium, nickel, titanium, and zinc, and their alloys. Although not as
strong as steels, certain nonferrous alloys have corrosion resistance and/or
strength-to-weight ratios that make them competitive with steels in
moderate-to-high stress applications. Many nonferrous metals have properties
other than mechanical that make them ideal for applications in which steel
would not be suitable.
The Light Metals: Aluminum and
Magnesium
Aluminum
► High electrical and thermal conductivity
► Corrosion resistance is excellent due to formation of a hard thin oxide surface film
► Very ductile metal, noted for its formability
► Pure aluminum is relatively low in strength, but it can be alloyed and heat treated to
compete with some steels, especially when weight is taken into consideration.
► Properties of Al alloys are influenced by work hardening and heat treatment, so
temper must be designated in addition to composition. This designation is attached to
the 4-digit code, separated by a hyphen, to indicate treatment or no treatment.
The Light Metals: Aluminum and
Magnesium
Magnesium Production
► Sea water contains about 0.13% MgCl - source of most commercially produced
2
magnesium. Sea water is mixed with milk of lime - calcium hydroxide (Ca(OH) 2).
The resulting reaction precipitates magnesium hydroxide (Mg(OH) 2) that settles and
is removed as a slurry. The slurry is then filtered to increase (Mg(OH) 2) content. The
slurry is mixed with hydrochloric acid (HCl), which reacts with the hydroxide to
form concentrated MgCl2. Electrolysis is used to decompose salt into magnesium
(Mg) and chlorine gas (Cl2). Magnesium is then cast into ingots for subsequent
processing. Chlorine is recycled to form more MgCl2.
Designation Scheme for Magnesium (Three-to-five character alphanumeric code)
► First two characters = letters that identify principal alloying elements (up to two
elements)
► Followed by a two-digit number that indicates, respectively, the amounts of the
two alloying ingredients to nearest percent
Example: AZ63A –aluminum 6%, zinc 3%, magnesium 91%
► Last symbol is a letter that indicates variation in composition or simply
chronological order in which alloy became commercially availability
► Magnesium alloys also require specification of a temper, and the same basic
scheme for aluminum is used for magnesium alloys
Copper
► Low electrical resistivity - commercially pure copper is widely used as an
electrical conductor excellent thermal conductor
Properties of Copper
► Strength and hardness of copper is relatively low; to improve strength, copper
is frequently alloyed
► Bronze - alloy of copper and tin (typically ~90% Cu, 10% Sn), widely used
today and in ancient times (i.e., the Bronze Age). Additional bronzes include
aluminum bronzes and silicon bronzes
► Brass - alloy of copper and zinc (typically ~65% Cu, 35% Zn).
► Highest strength alloy is beryllium-copper (only about 2% Be), which can be
heat treated to high strengths and used for springs
Nickel and Its Alloys
- similar to iron in some respects:
► Magnetic
► Modulus of elasticity is approximately same for iron and steel
► Much more corrosion resistant - widely used as (1) an alloying
element in steel, e.g., stainless steel, and (2) as a plating metal
on metals such as plain carbon steel
► High temperature properties of alloys are superior
► Alloys of nickel are commercially important and are noted for
corrosion resistance and high temperature performance
► In addition, a number of superalloys are based on nickel
Titanium and Its Alloys
► density of Ti is between aluminum and iron
► light weight and good strength-to-weight ratio (thus used in aerospace applications)
Properties of Titanium
► Coefficient of thermal expansion is relatively low among metals
► Stiffer and stronger than Al
► Retains good strength at elevated temperatures
► Pure Ti is reactive, which presents problems in processing, especially in molten state
► At room temperature Ti forms a thin adherent oxide coating (TiO 2) that provides
excellent corrosion resistance
Applications of Titanium
► In the commercially pure state, Ti is used for corrosion resistant components, such as
marine components and prosthetic implants
► Titanium alloys are used as high strength components in temperatures ranging from
ambient to above 550°C (1000°F), especially where its excellent strength-to-weight
ratio is exploited
► Alloying elements used with titanium include aluminum, manganese, tin, and vanadium
Zinc and Its Alloys

► Low melting point makes it attractive as a casting metal,

especially die casting
► Also provides corrosion protection when coated onto steel
or iron
► The term galvanized steel refers to steel coated with zinc
► Widely used as alloy with copper (brass)
Lead and Tin
-often considered together because of their low melting
temperatures and use as soldering alloys

Lead - dense, low melting point; low strength, low hardness, high
ductility, good corrosion resistance
► Applications: solder, plumbing pipes, bearings, ammunition, type
metals, x-ray shielding, storage batteries, and vibration damping

Tin - even lower melting point than lead; low strength, low
hardness, good ductility
► Applications: solder, bronze, "tin cans" for storing food
Refractory Metals
Molybdenum
► Used as a pure metal (99.9+% Mo) and alloyed
► Properties: high melting point, stiff, strong, good high temperature strength
► Applications: heat shields, heating elements, electrodes for resistance welding, dies for high
temperature work (e.g., die casting molds), and parts for rocket and jet engines. Also widely
used as an alloying ingredient in steels and superalloys
Tungsten
► Properties: highest melting point among metals, one of the densest, also the stiffest (highest
modulus of elasticity) and hardest of all pure metals
► Applications typically characterized by high operating temperatures: filament wire in
incandescent light bulbs, parts for rocket and jet engines, and electrodes for arc welding. Also
widely used as an element in tool steels, heat resistant alloys, and tungsten carbide
Columbium
Tantalum
Superalloys
Superalloys - high-performance alloys designed to meet demanding requirements
for strength and resistance to surface degradation at high service temperatures
► Many superalloys contain substantial amounts of three or more metals, rather
than consisting of one base metal plus alloying elements.
► Commercially important because they are very expensive.
► Technologically important because of their unique properties.
► Room temperature strength properties are good but not outstanding.
► High temperature performance is excellent – tensile strength, hot hardness,
creep resistance, and corrosion resistance at very elevated temperatures.
► Operating temperatures often in the vicinity of 1100°C (2000°F)
strengthening is done by precipitation hardening.
► Applications: gas turbines - jet and rocket engines, steam turbines, and
nuclear power plants – systems in which operating efficiency increases with
higher temperatures
Three Groups of Superalloys

1. Iron-based alloys - in some cases iron is less than 50% of total

composition

2. Nickel-based alloys - better high temperature strength than

alloy steels
Other elements: Cr, Co; also: Al, Ti, Mo, and Fe

3. Cobalt-based alloys ≈40% Co and ≈20% chromium

Other alloying elements include Ni, Mo, and W
Shaping, Assembly, and Finishing Processes
for Metals

► Metals are shaped by all of the basic processes: casting, powder

metallurgy, deformation, and material removal
► Metal parts are joined to form assemblies by welding, brazing and
soldering, and mechanical fastening
► Heat treating is performed to enhance properties
► Finishing processes (e.g., electroplating and painting) are commonly
used to improve appearance of metal parts and/or to provide
corrosion protection
Methods to Enhance Mechanical Properties
in Metals

► Alloying - important technique to strengthen metals

► Cold working - strain hardening during deformation to increase strength (also
reduces ductility). Strengthening of the metal occurs as a byproduct of the
forming operation
► Heat treatment - heating and cooling cycles performed on a metal to
beneficially change its mechanical properties. They operate by altering the
microstructure of the metal, which in turn determines properties.
Methods to Enhance Mechanical Properties
in Metals

Types of Heat Treatments to improve quality:

❑ Normalizing - The material is heated to between 750-980 °C then cooled at
room temperature; product: high strength and high ductility, tougher than
annealed steel.
❑ Annealing – heating above the critical temperature then controlled cooling
inside a furnace.
During normalizing, thinner pieces will cool faster in the air and become
harder than thicker pieces. But, with annealing and its furnace cooling, the
hardness of both thick and thin parts will be comparable.
❑ Quenching – heating then rapid cooling in water or oil, for hardening steel.
❑ Tempering – reheating below critical temperature, holding the temperature
for a specific period, then then slowly cooling in still air.
Microstructure of Cast Iron