Light Metals and Alloys

Introduction
• Light metals and their alloys are materials of relatively low density and high

strength-to-weight ratio.
• Aluminium, magnesium, and titanium are light metals of significant
commercial importance.
• Aluminium is the most versatile.
• Magnesium has the lowest density.
• Titanium is the most corrosion-resistant.

Relative bulk densities of metallic alloys

 •#1 Aluminum – 65% lighter than steel
•#2 Magnesium – 77% lighter than steel
•#3 Titanium – 42% lighter than steel

Tensile strength Specific Strength

Materials Density (g/cc)
(MPa) (kN.m/kg)

Low carbon steel (AISI

365 7.87 46.4
1010)

Stainless steel (304) 505 8.00 63.1

Titanium 344 4.51 76

Aluminium alloy (6061-T6) 310 2.70 115

Magnesium alloy 275 1.74 158

Aluminium alloy (7075-T6) 572 2.81 204

Strength vs density materials selection chart (Adapted from M. F. Ashby)
#1 Aluminium
• Aluminum is the most widely used non-ferrous metal in the world.
• Aluminum offers great corrosion resistance, and some alloys can offer strength
that approaches that of carbon steel.
• Despite being more costly than steel, aluminum is cheaper than both
magnesium and titanium.
• Aluminum offers very high formability and machinability, good weldability,
and high ductility.
• It has both high thermal and electrical conductivity.
• Despite this, it is susceptible to wear, has a lower strength-to-weight ratio
than titanium, and does not perform well at high temperatures.
• Aluminum and magnesium have similar melting points at 660°C (1220°F) and
650°C (1202°F), respectively.
Aluminum has a vast number of
applications, some of which include:
•Electronics components and electrical
wiring.
•Heat sinks for efficient heating and
cooling
•Aircraft fuselages and numerous
other aerospace components.
•Durable, cost-effective consumer
products like furniture and cookware.
•Architectural elements, such as railings
and siding
•Cast aluminum and extruded
aluminum automotive parts
#2 Magnesium
• More expensive than aluminum, but cheaper than titanium alloys,
• magnesium is used as the base for the lightest structural alloys around.
• Magnesium on its own is vulnerable to corrosion and chemical degradation,
and
• it also offers a lower strength than the other light metals.
• However, modern magnesium alloys and coating techniques are helping to
improve the strength and of magnesium products durability.
• Magnesium offers high machinability but is generally only machined by
specialist shops as it has the danger of highly combustible magnesium dust.
• It also offers a unique damping ability that makes it useful for mitigating
vibrations on sensitive equipment.
Most magnesium applications are geared
toward taking advantage of its extremely
lightweight (1.74g/cm³), including:
•Components of consumer products like
luggage, ladders, and cameras
•High-performance sporting and recreational
equipment, like bicycle frames
•Weight-reducing parts in military gear and
equipment
•Performance automotive parts, like
magnesium alloy wheels and gearboxes
#3 Titanium

• Titanium is the strongest metal on this list by far.

• It also has excellent corrosion resistance, performs well at high temperatures,

and works well for implants due to its high biocompatibility.

• Titanium is the heaviest of the three lightweight metals on our list at 4.51 g/cm³.

• It’s also the most expensive and the most challenging to machine.

• Therefore, titanium is often reserved for more demanding applications that

require a more robust material.

Common applications for titanium
can include:
•Chemical processing equipment that
requires a high chemical resistance.
•Long-lasting medical implants,
devices, and prosthetics.
•Strong and lightweight aerospace
components.
•Corrosion-resistant marine and
military equipment.
 What is Strength-to-Weight Ratio?
• Strength to weight ratio is a measure of the strength of an object divided by its
mass or weight.
• It is used to determine the efficiency and performance of any given material or
component.
• Strength-to-weight ratio is essential for assessing how much use a certain
structure can take while making sure the weight limit isn’t exceeded.
• It helps engineers to craft designs with optimal strength and mass characteristics.
• With a proper understanding of strength-to-weight ratios, Engineers can create
designs that perform effectively under a variety of conditions with utmost
confidence and efficiency.
• By optimizing the ratio, engineers can save costs associated with materials that
lack the required strength for a specific application, as well as increase efficiency
and performance.
 Strength-to-Weight Ratio Factors

• Strength-to-weight ratio is affected by various materials and components such

as metals, carbon fiber and composites, wood, plastics, ceramics, and glass.
• Factors such as modulus of elasticity, yield stress, ultimate tensile strength, and
strain hardening rate also affect the strength-to-weight ratio.
• Metals are usually the most commonly used material in engineering projects
due to their high strength-to-weight ratio.
• Carbon fiber and composites can also be very light while providing excellent
strength and durability.
• Wood can provide good strength at a relatively low weight, but it can be prone
to warping and shrinkage.
• Plastics tend to have lower strength-to-weight ratios than metals and are more
susceptible to damage from UV exposure.
• Ceramics generally have low strengths combined with heavy weights but
can be useful for applications that require insulation or heat resistance.
• Glass also tends to have a lower strength-to-weight ratio than metals but
has great resistance to corrosion and abrasion.
Production of Aluminium
• Difficult in extracting Al from its ores (Al2O3) as it combines so strongly
with oxygen that it cannot be reduced with carbon.
• Aluminium was first isolated in 1809 in England by Sir Humphry Davy
which he produced from alum.
• In 1886, Hall in the United States and Héroult in France led to the
development of an economic method for the electrolytic extraction of
relatively high-purity aluminium which remains the basis for production
today.
• The principal aluminium-bearing minerals in bauxite exist as several
forms of hydrated aluminium oxide, notably gibbsite (Al2O3·3H2O),
which is also known as hydragillite or trihydrate, and boehmite
(Al2O3·H2O) also known as monohydrate.
• Bauxite ore bodies typically contain 30–60% hydrated Al2O3 together with
impurities comprising mainly iron oxides and silica.
• Immense amounts of aluminium are also present in clays, shales, and
other minerals.
• The amphoteric nature of aluminium provides the opportunity to use
acidic as well as alkaline processes for its recovery.
• Acid extraction of alumina from kaolinite clay mineral and is a major
constituent of the ash in coal.
• The minerals, nepheline, Na3K(AlSiO4)4, and alunite, KAl3(SO4)2(OH)6, are
processed commercially.
• Alumina obtained from these and other alternative sources is 1.5–2.5
times more costly than that produced from the Bayer process.
Bayer process for alumina recovery
• The Bayer process was developed and patented by Karl Josef Bayer in
Austria in 1888.
• It involves digesting crushed bauxite in strong sodium hydroxide solutions
at temperatures up to 240°C

First stage of the Bayer process can be expressed by the equation:

Al2O3. xH2O + 2NaOH 2NaAlO2 + (x +1)H2O
Second stage:
2NaAlO2 + 2H2O 2NaOH + Al2O3 .3H2O
Reverse reaction is achieved by cooling the liquor and seeding with crystals of
the trihydrate, Al2O3·3H2O, to promote precipitation of this compound as fine
particles rather than in a gelatinous form.
Hall-Héroult smelting process
• Production of aluminium lies in dissolving the oxide in molten cryolite (Na3AlF6)
and a typical electrolyte contains 80–90% of this compound and 2–8% of alumina,
together with additives such as AlF3 and CaF2.
• An electrolytic-reduction cell consists essentially of baked carbon anodes that are
consumed and require regular replacement, the molten cryolite–alumina
electrolyte, a pool of liquid aluminium, a carbon-lined container to hold the metal
and electrolyte.
• A typical modern cell is operated at around 950°C and takes up to 500 kA at an
anode current density around 0.7 A cm−2.
• The molten aluminium is siphoned out regularly to be cast into ingots and alumina
is replenished as required.
• The mechanism for the electrolytic reaction in a cell remains uncertain but it is
probable that the current-carrying ions are Na+, AlF4-, AlF63- and one or more
ternary complex ions such as AlOF32-.
Hall-Héroult smelting process
Production of Magnesium
• Magnesium metal was first isolated in 1828 by the Frenchman Antoine-Alexander
Bussy who fused MgCl2 with metallic potassium.
• First production of magnesium by the electrolytic reduction of the chloride was
accomplished by Michael Faraday in 1833.
• The most common surface minerals are the carbonates dolomite (MgCO3·CaCO3) and
magnesite (MgCO3).
• Mineral brucite (MgO·H2O) is somewhat rarer, as are the chlorides of which
carnallite (MgO·KCl·6H2O) is one example.
• Seawater provided more than 80% of the world’s supply of this metal which was
extracted by the electrolytic reduction of molten MgCl2.
• Two processes have been developed to produce magnesium by the direct reduction of
dolomite by ferrosilicon at high temperatures.
One is the Pidgeon process originating from Canada in 1941 in which this reaction is
carried out in the solid state. The other is the Magnétherm process that was developed
in France and which operates at much higher temperatures so that the reaction mixture is
liquid.
Electrolytic extraction of magnesium
Two types of electrolytic processes have been used to produce magnesium that differ in
the degree of hydration of the MgCl2 and in cell design. One was pioneered by IG Farben
industrie in Germany in 1928 known as IG process.
• It uses dry MgO derived from minerals in seawater which is briquetted with a reducing
agent, e.g., powdered coal, and MgCl2 solution.
• The briquettes are lightly calcined and then chlorinated at around 1100°C to produce
anhydrous MgCl2, which is fed directly into the electrolytic cells operating at 740°C.
• Each cell uses graphite anodes that are slowly consumed and cast steel cathodes that
are suspended opposite one another.
• Magnesium is deposited on the cathodes as droplets which rise to the surface of the
electrolyte, whereas chlorine is liberated at the anodes and is recycled to produce
the initial MgCl2 cell feedstock.
Cathode: Mg2+ + 2e → Mg(l) (1)
Anode: 2 Cl- → Cl2(g) + 2e (2)
Overall: MgCl2(s) → Mg(l) + ½ Cl2(g) (3)
The second electrolytic process for extracting magnesium from seawater was
developed by the Dow Chemical Company
• Magnesium in MgCl2 was precipitated as the hydroxide by the addition of lime and
then dissolved in HCl. This solution was then concentrated and dried although the
process stopped short of complete dehydration of the MgCl2 which was then
available as the cell electrolyte.
• The energy consumed per kg of magnesium produced was around 12.5 kWhfor the
Norsk Hydro cell and 17.5 kWh for the Dow cell. However, each process required
the additional consumption of approximately 15 kWh of energy per kg for
preparation of MgCl2 cell feed.
Two new processes developed: Canada and Australia to produce basic feedstock
anhydrous MgCl2 in a high-purity form for use in electrolytic cells
• Magnola process used tailings from asbestos mines to take advantage of magnesium
silicate contained in serpentine ore.
• The tailings were leached in strong HCl by means of a novel procedure to produce a
solution of MgCl2 which was purified by adjusting the pH.
• Ion exchange techniques were then used to generate concentrated, high-purity brine
that was dehydrated for use in an electrolytic cell.
Australian process was developed to exploit magnesite (MgCO3) mined from a huge
surface deposit in Queensland.
• MgCl2 was leached from the magnesite with HCl and glycol was added to the
solution, after which water was removed by distillation.
• Magnesium chloride hexammoniate was then formed by sparging with ammonia.
Final calcining produced a relatively low-cost, high-purity MgCl2, and the solvent
and ammonia were recycled.
Thermic processes

Production of magnesium by direct thermal reduction of calcined dolomite with

Ferrosilicon.
2 CaO.MgO(s) + (x Fe) Si(s) = 2 Mg(s) + 2 Ca2SiO4(s) + Fe(s)

Pidgeon process

Schematic-Flowsheet-of-the-Pidgeon-Mayer-1944
• Around 150 kg briquettes of the reactants into each tubular steel retorts
• Typically 250–300 mm in diameter and 3 m long.
• Evacuated to a pressure of below 0.1 torr and externally heated to a temperature in the
range 1150–1200°C,
• Magnesium forms as a vapor that condenses on removable water-cooled sleeves at the
ends of the retorts that are located outside the furnace
• Approximately 1.1 tonnes of ferrosilicon is consumed for each tonne of magnesium
produced.
Advantages of the Pidgeon process are
• relatively low capital cost and the
• less stringent requirement on the purity of the raw materials.
Major deficiencies are
• labor-intensive, low productivity, high energy consumption,
• batch process, only produces about 20 kg of magnesium from each retort, and
• lengthy cycle time of around 8 h.
• Retorts must then be emptied, cleaned, and recharged that may be dusty and unpleasant.
Magnétherm process
• Uses an electric arc furnace operating at around 1550°C and with an internal pressure
of 10–15 torr.
• Reaction takes place in the liquid phase, the time required for its completion is less.
• Furnace may be charged continuously and discharged at regular intervals, and
alumina is added to the dolomite/ferrosilicon charge.
• Magnesium is again produced as a vapor which is solidified in an external condenser.
• Batch sizes may be as high as 11,000 kg.

Mintek Process
• Large scale batch silicothermic process operating at atmospheric pressure.
• It attempts to overcome the productivity and operational difficulties associated with
large batch process called the Magnetherm process.
• Utilization of slag and aluminium, in addition to ferrosilicon, for the reduction of
magnesium oxide at higher temperatures, 1700 to 1750oC.
• Vapour pressure of magnesium is much higher, at about 0.85 atm.
• has higher productivity (100 tonnes), magnesium purity of 97.86 wt%.
Production of Titanium
Titanium is the ninth most abundant element in the earth’s crust with its two prime sources
being the minerals rutile (TiO2) and ilmenite (FeO·TiO2).
Relatively pure but less ductile titanium was first produced in 1910 in the United States by
Matthew A. Hunter, who reacted titanium tetrachloride (TiCl4) with molten sodium under
vacuum:
TiCl4 (g) + 4Na(l) 4NaCl(l) + Ti(s) at 700 − 800°C
• A. E. van Arkel and J. H. de Boer succeeded in dissociating titanium tetraiodide (TiI4) on
a hot tungsten filament (1400°C) in an evacuated glass bulb.
• Ultrapure titanium hairpins thus produced turned out to be very ductile and soft at room
temperature.
• In 1932, Wilhelm Kroll, in Luxembourg, invented the process of producing ductile
titanium by reacting TiCl4 with molten calcium.
• TiCl4 can be made from both rutile and by the following exothermic chlorination process:
TiO2 (impure) + 2C + 2Cl2 TiCl4 + 2CO + Q(heat) at 1000 −1100°C
• The TiCl4 produced (≥98% purity) contains a variety of impurities including SiCl4,
VOCl3, and FeCl3, and is subsequently purified to more than 99.9% purity by a series
of processes.
• Magnesium ingot 99.9% purity are melted and used to reduce the high-purity TiCl4 in
a high-purity argon atmosphere.
• During subsequent vacuum distillation at 900–1000°C, the Mg (l) and MgCl2 (l)
entrapped in the titanium vaporize due to their high vapor pressures. The resulting
titanium product is porous and is referred to as Titanium sponge.
• Only 10-15% of the TiCl4 production is used for titanium production.
• The remainder is converted back into pure white pigment TiO2 in paint through direct
oxidation of TiCl4 as the mineral rutile is impure.

TiCl4 + O2 = TiO2 + 2Cl2

The Kroll titanium sponge production process consists of four essential steps:
(1) chlorination or production of titanium tetrachloride,
(2) purification of titanium tetrachloride,
(3) reduction with molten magnesium, and
(4) vacuum distillation of the reaction products.
• Pure titanium ingots are made by arc melting titanium sponge or scrap, in a vacuum or
inert environment.
Consumable-electrode vacuum arc remelting (VAR) process,
• The consumable electrode in this process is made from compacts of titanium sponge and
scrap formed using a large press, which are joined together by plasma arc welding.
• Only two solid materials (yttrium oxide and molybdenum) are known to be relatively inert
to molten titanium: suitable crucible material.
• water-cooled copper crucibles are normally used to solidify the melted sponge.
Electron beam cold hearth remelting (EBCHR)
• Completely melting titanium sponge or scrap
• Eliminating the need to fabricate consumable electrodes
• It can produce homogeneous round and square titanium ingots by single melting,
• It can effectively remove both the high-density inclusions (e.g., containing tungsten,
tantalum, or molybdenum) and low-density inclusions (e.g., titanium nitride), because the
higher temperatures and longer residence times offer a greater opportunity for these
inclusions to be dissolved or removed.
Plasma arc melting process
• Melt titanium and its alloys under an inert argon or helium atmosphere.
• Suited for fabricating titanium alloys containing alloying elements with greatly
dissimilar melting points and vaporization pressures.
• Effectively eliminate high-density inclusions.
• Enable high-quality titanium alloys for demanding applications.
UNIT 2: Al Alloys
Al alloy Categories.
Aluminum alloys divided into two major categories:
1. wrought alloys and
2. cast alloys
Based on the primary mechanism of property development further categorise as
• Heat treatable
• Non heat treatable.
Cast and wrought alloy nomenclatures have been developed. The Aluminum Association
system is most widely recognized in the United States.
For wrought alloys a four-digit system is used to produce a list of wrought composition
families as follows:
1xxx: Controlled unalloyed (pure) composition, used primarily in the electrical and
chemical industries.
2xxx: Copper is the principal alloying element, although other elements, like magnesium,
may be specified. Widely used in aircraft where their high strength (yield strengths as high as
455 MPa, or 66 ksi) is valued.
3xxx: Manganese is the principal alloying element, used as general-purpose alloys for
architectural applications and various products.
4xxx: Silicon is the principal alloying element, used in welding rods and brazing sheet.
5xxx: Magnesium is the principal alloying element, used in boat hulls, gangplanks, and
other products exposed to marine environments.
6xxx: Magnesium and silicon are the principal alloying elements, commonly used for
architectural extrusions and automotive components.
7xxx: Zinc is the principal alloying element (although other elements, such as copper,
magnesium, chromium, and zirconium, may be specified), used in aircraft structural
components and other high-strength applications.
The 7xxx series are the strongest aluminum alloys, with yield strengths 500 MPa (73
ksi) possible.
8xxx: Alloys characterizing miscellaneous compositions. The 8xxx series alloys may
contain appreciable amounts of tin, lithium, and/or iron.
9xxx: Unused
Wrought alloys that constitute heat-treatable (precipitation-hardenable) aluminum
alloys include the 2xxx, 6xxx, 7xxx, and some 8xxx alloys.

Table 1 Classification of wrought aluminum alloys

according to their strengthening mechanism
Alloy system Aluminum series
Work-hardenable alloys
Pure Al 1xxx
Al-Mn 3xxx
Al-Si 4xxx
Al-Mg 5xxx
Al-Fe 8xxx
Al-Fe-Ni 8xxx
Precipitation-hardenable alloys
Al-Cu 2xxx
Al-Cu-Mg 2xxx
Al-Cu-Li 2xxx
Al-Mg-Si 6xxx
Al-Zn 7xxx
Al-Zn-Mg 7xxx
Al-Zn-Mg-Cu 7xxx
Al-Li-Cu-Mg 8xxx
Cast alloys are described by a three-digit system followed by a decimal value.
1xx.x: Controlled unalloyed (pure) compositions, especially for rotor manufacture
2xx.x: Copper is the principal alloying element. Other alloying elements may be specified.
3xx.x: Silicon is the principal alloying element. The other alloying elements such as
copper and magnesium are specified. 3xx.x series comprises nearly 90% of all shaped
castings produced.
4xx.x: Alloys in which silicon is the principal alloying element.
5xx.x: Alloys in which magnesium is the principal alloying element.
6xx.x: Unused
7xx.x: Alloys in which zinc is the principal alloying element. Other alloying elements such
as copper and magnesium may be specified.
8xx.x: Alloys in which tin is the principal alloying element.
9xx.x: Unused

Heat-treatable casting alloys include the 2xx, 3xx, and 7xx series
Aluminium alloys and temper designations
Non-heat-treatable alloys
• Non-heat-treatable alloys cannot be strengthened by heat treatment.
• Alloys of 1xxx, 3xxx, 4xxx and 5xxx series are non-heat-treatable.
• Cast alloys of 1xx, 4xx and 5xx series are non-heat-treatable.
• Initial strength of these alloys is achieved due to the hardening effect
of the alloying elements: manganese (Mn), silicon (Si), magnesium
(Mg).
• Additional hardening of these alloys is done by cold work (strain
hardening).
• Non-heat-treatable alloys are ductile and moderately strong
(depending on the alloying elements concentration)
Heat-treatable alloys
• It can be strengthened by heat treatment.
• Alloys of 2xxx, 6xxx and 7xxx series are heat-treatable.
• Heat-treatable casting alloys include the 2xx, 3xx, and 7xx series
• The initial strength of these alloys is achieved due to the hardening effect
of the alloying elements: copper (Cu), silicon (Si), magnesium (Mg) and
zinc(Zn).
• Intermetallic compounds formed from these elements, harden the alloys
from this group by a heat treatment, called precipitation hardening (age
hardening)
• Precipitation hardening (age hardening) – strengthening by precipitation
of fine particles of a second phase from a supersaturated solid solution.
Precipitation hardening heat treatment involves the following stages:
Solution treatment
• heated to a temperature above the solvus temperature to dissolve the
second phase in the solid solution.
• hold at this temperature for a time varying from 1hour to 20 hrs. until
the dissolving has been accomplished.
• The temperature and the soaking time of solution treatment should
not be too high to prevent excessive growth of the grains.
Quenching
• Quenching is carried out in water, water-air mixture or sometimes in
air.
• Obtaining supersaturation solid solution at room temperature.
• Since the second phase retains dissolved at this stage, hardness of the quenched
alloy is lower than after age precipitation, higher than in annealed state.
Aging
• Depending on the temperature at which this operation is carried out aging may
be artificial or natural.
Artificial aging
• Heated up to a temperature below the solvus temperature, followed by soaking
for a time varying between 2 to 20 hours.
• Soaking time depends on the aging temperature.
• Aging temperature and the soaking time are also determined by the desired
resulted combination of the strength and ductility.
Natural aging
• Natural aging is conducted at room temperature and it takes a relatively long
period of time
 Effects of alloying elements on properties of aluminum alloys
Alloying elements when added to Aluminum alloys may produce effects
of precipitation hardening (age hardening), solid solution
hardening, dispersion strengthening, grain refining, modifying metallic
and intermetallic phases, suppression of grain growth at elevated
temperatures (e.g. during annealing), wear resistance and
other tribological properties.
Silicon, Si (up to 17%)
• Improves castability of aluminum alloys due to a better fluidity and
lower shrinkage of molten aluminum-silicon alloys.
• Increases strength of the alloys.
• Improves resistance to abrasive wear.
 • Silicon in a combination with magnesium allows to strengthen the
alloys by precipitation hardening heat treatment.
(Wrought aluminum-magnesium-silicon alloys (6xxx), Cast aluminum
alloy 356.0).
Copper, Cu (up to 6.5%)
• Increases tensile strength, fatigue strength and hardness of the alloys
due to the effect of solid solution hardening.
• Allows to strengthen the alloys by precipitation hardening heat
treatment.
(Wrought aluminum-copper alloys (2xxx), Cast aluminum alloy 201.0).
• Decreases the ductility of the alloys.
• Decreases corrosion resistance.
Magnesium, Mg (up to 10%)
• Strengthens and hardens the alloys by solid solution hardening
mechanism without considerable decrease of ductility
• (Wrought aluminum-magnesium alloys (5xxx), Cast aluminum alloy 518.0.
• In a combination with silicon or zinc allows to strengthen the alloys by
precipitation hardening heat treatment
(Wrought aluminum-magnesium-silicon alloys (6xxx), Wrought aluminum-
zinc-magnesium alloys (7xxx), Cast aluminum alloy 356.0, Cast aluminum
alloy 713.0)
•Manganese, Mn (up to 1.5%)
• Strengthens and hardens the alloys (Wrought aluminum-manganese
alloys (3xxx)) by solid solution hardening and dispersion hardening
mechanisms.
 • Improves low cycle fatigue resistance.
• Increases corrosion resistance.
• Improves ductility of aluminum alloys containing iron and silicon due
to modification of Al5FeSi intermetallic inclusions from platelet to
cubic form Al15(MnFe)3Si2.
Zinc, Zn (up to 8%)
• In a combination with magnesium or magnesium-copper allows to
strengthen the alloys by precipitation hardening heat treatment
(Wrought aluminum-zinc-magnesium alloys (7xxx), Cast aluminum
alloy 713.0).
• Increases susceptibility of the alloys to Stress corrosion cracking.
Chromium, Cr (up to 0.3%)
• Suppresses the grain growth at elevated temperatures (e.g. during
heat treatment).
• Improves ductility and toughness of aluminum alloys containing iron
and silicon due to modification of Al5FeSi intermetallic inclusions
from platelet to cubic form (similar to the effect of manganese).
• Reduces susceptibility of the alloys to Stress corrosion cracking.
Nickel, Ni (up to 2%)
• Increases hardness and strength of aluminum-copper (Wrought
aluminum-copper alloys (2xxx) and aluminum-silicon (Wrought
aluminum-silicon alloy 4032) at elevated temperatures.
• Reduces the Coefficient of Thermal Expansion.
Lithium, Li (up to 2.6%)
• Increases strength by the precipitation hardening heat treatment.
• Increases Modulus of Elasticity.
• Reduces density.
Titanium, Ti (up to 0.35%)
• Refines primary aluminum grains (grains formed during
the Solidification) due to formation of fine nuclei Al3Ti.
• Titanium is commonly added to aluminum alloys together with
boron due to their synergistic grain refining effect.
Boron, B (up to 0.03%)
• Boron in a combination with titanium refines primary aluminum
grains (grains formed during the Solidification) due to formation
of fine nuclei TiB2.
Zirconium, Zr (up to 0.3%); Vanadium, V (up to 0.2%)
• Inhibit recovery and recrystallization
• Increase the recrystallization temperature.
Iron, Fe (up to 1.1%)
• Increases strength due to formation of Al-Fe intermetallics.
• Decreases ductility. In most aluminum alloys Iron is
undesirable impurity.
Sodium, Na (up to 0.015%); Antimony, Sb (up to 0.5%); Calcium,
Ca (up to 0.015%), Strontium, Sr (up to 0.05%)
• Increase ductility of hypoeutectic and eutectic aluminum-
silicon alloys (Wrought aluminum-silicon alloys (4xxx), Cast
aluminum alloy 443.0) by a modification of the silicon phase
from coarse platelet like particles to fine fibrous structure.
 Phase diagram

• A phase diagram is a temperature - composition map which indicates the phases

present at a given temperature and composition.
• It is determined experimentally by recording cooling rates over a range of
compositions.
• We will use these diagrams to understand and predict the alloy microstructure
obtained at a given composition.
Al-Si phase diagram:
• Aluminium has zero solid
solubility in silicon at any
temperature. This means
that there is no beta phase
• Al-Si alloys, the eutectic
composition is a structure
of α-Al+Si rather than
alpha+beta.

• Consider two Al-Si alloys, both of composition 13wt%Si.

• The second alloy, though, will be "doped" with a very small amount of Sodium
(0.01%Na).
• Two alloys are : (1) Al-13wt%Si (2) Al-13wt%Si-0.01%Na
• Al-13wt%Si alloy is hypereutectic.
• Eutectic in phase diagram contains much more α-Al than Si and eutectic mixture
(α-Al +Si) to be mainly alpha.
• As this alloy is hypereutectic, primary Si forms first, depleting the liquid of Si
until it reaches the eutectic composition where the remaining solidification
follows the eutectic reaction.
• The primary Si has a cuboidal form.
• The eutectic mixture, though, is non-
lamellar in form and appears, in section, to
consist of separate flakes
• These coarse flakes of Si in the eutectic
promote brittleness within these alloys.
Most Al-Si alloys used have a near-eutectic
composition since this gives a lower melting
point and makes them cheaper to cast.
• Adding a small quantity of a ternary element, here Sodium, causes modification
of the microstructure.
• This addition effectively moves the eutectic point to a higher silicon
concentration and lower temperature.
• This modifies the growth of the eutectic silicon to produce an irregular fibrous
form rather than the usual flakes.

• The eutectic point has

moved far enough to
make the alloy, at this
composition, hypo-
eutectic instead of
hyper-eutectic.
• Primary alpha forms,
rather than primary Si.
• Adding a very small impurity of 0.01%Na the microstructure of the alloy is
changed and its properties are greatly improved.
• Using phase diagrams to improve our understanding of these mechanisms
we can more easily predict the effects of compositional changes.
a b

c d
Al-Cu phase diagram
Al-Cu phase diagram shown only goes up to around 60%, by weight, of Copper.
The Al-Cu phase diagram is split at around 54wt%Cu by a particular phase.
Consider two Al-Cu alloys, one of composition 33wt%Cu and the other of
20wt%Cu.Examining the phase diagram:
• 33wt%Cu alloy is of eutectic composition and
• 20wt%Cu alloy is hypoeutectic as it is to the left of the eutectic point.
 The eutectic reaction, at 33%Cu can be shown as:

Liquid α+ɵ
• Two phases grow simultaneously as an interconnected structure - the eutectic
phase.
• The lamellar nature of the eutectic mixture as it solidifies ensures that diffusion
fields ahead of the liquid-solid interface are limited
• The Al-20wt%Cu alloy is hypoeutectic. The liquid alloy initially contains a higher
percentage of Al than that corresponding to the eutectic composition; the primary
solid phase that forms is α-Al.
• Formation of the alpha phase, however, depletes the remaining liquid in
Aluminium (Al) and the liquid composition shifts toward the eutectic
composition.
• When the composition reaches eutectic (33%Cu for this phase diagram) the
remaining liquid follows the eutectic reaction.
• Microstructure consists of primary alpha dendrites surrounded by a finely

divided eutectic mixture of two solid phases (alpha+theta).

• Microstructural changes strongly influence the engineering properties of an

alloy. The lamellar nature of the eutectic phase, impedes dislocation

movement through the alloy.

• If dislocations cannot move easily then the material won't yield until a higher

stress is applied, i.e. the strength of the alloy is increased.

• Understanding how phase diagrams work we can predict and refine alloys

to give us the properties we require.

Micrograph of Al-33%wtCu alloy Micrograph of Al-20%wtCu alloy
Alloy
Al–Cu
Precipitates
GP zones as
Remarks
Usually single layers of
αss GP zones ɵ" ɵ ' ɵ
thin plates copper atoms on
on {100}α {100}α.

θ″ (formerly Coherent, probably two

GP zones layers of copper atoms
separated by three layers
of aluminium atoms. May
be nucleated at GP zones
θ′ tetragonal Semi-coherent plates
Al2Cu nucleated at dislocations.
a = 0.404 nm Form on {100}α
c = 0.580 nm
θ body- Incoherent equilibrium
centered phase.
tetragonal May nucleate at surface
Al2Cu of θ′.
a = 0.607 nm
c = 0.487 nm
Crystal structures of (A) GP zones, (B) θ″, (C) θ′,
and (D) θ (Al2Cu) that may precipitate in aged
binary Al–Cu alloys.
Al-Mg phase diagram
Al-Mg alloy
• Al-Mg alloys of the 5xxx series are strain hardenable and have moderately high
strength, excellent corrosion resistance even in salt water, and very high
toughness even at cryogenic temperatures
• 5xxx alloys find wide application in building and construction, highways
structures including bridges, storage tanks and pressure vessels, cryogenic
tankage and systems for temperatures as low as -270°C (near absolute zero), and
marine applications.
• Magnesium has significant solubility (17%) in aluminum and imparts substantial
solid solution strengthening (which can also contribute to enhanced work
hardening characteristics).
• The 5xxx series alloys (containing <~6% Mg) do not age harden. Whilst it is
possible for β-phase (Mg2Al3) to precipitate in systems with above ~3%Mg, the
β-phase is not a strengthening precipitate and actually weakens the alloy.
• Fully work-hardened AA5456 (Al-4.7Mg-0.7Mn-0.12Cr) has a tensile strength of
>380MPa.
• One issue with fully work-hardened 5xxx series alloys is that the heavy
dislocation density (and supersaturation of the solid solution with Mg) can
permit the sensitization of the microstructure by precipitation of deleterious β-
phase (Mg2Al3) during sustained high-temperature exposure.

• Mg has a high solubility in solid

solutions and therefore it provides the
most effective enhancement of
strength among all alloying additions
in the aluminum solid solution.
• Mg has a strong influence on
recrystallization and grain growth
• Small additions of chromium and manganese, which are present in most alloys
and raise the recrystallization temperatures, also increase tensile properties for
a given magnesium content.
• 5xxx series aluminum-based alloys are currently being used as automotive BIW
materials.
• Al-Mg alloys used in BIW applications have very good formability, relatively low
yield stress and work harden during cold working.
• Strength values in the annealed condition range from 40 MPa yield and 125 MPa
tensile for Al–0.8Mg (5005) to 160 MPa yield and 310 MPa tensile for the strongest
alloy 5456.
• If the magnesium content exceeds 3–4%, there is a tendency for the β phase,
Mg5Al8, to precipitate in slip bands and grain boundaries which may lead to
intergranular attack and SCC in corrosive conditions.

Microstructure of Al-Mg alloy

Microstructure of as-cast Al-Mg-Si alloys with (a) 0.008 wt.% Ti and (b) 0.20
wt.% Ti

Shouxun Ji et al., Materials Science Forum 2013, 765:23-27

 Al-Mg2Si
• 6xxx series contain silicon and magnesium
approximately in the proportions required for
formation of magnesium silicide (Mg2Si), thus
making them heat treatable.

Microstructure of A. Al-10wt.% Mg2Si,

B. Al-15wt.% Mg2Si
Phase diagram of Al-Mg2Si
• Mg and Si additions decreased the microstructural inhomogeneity by
producing a better distribution of primary α-Al and Al–Mg2Si eutectics, but had
contrary effects on eutectic Mg2Si morphology.
• Increasing Mg level transformed eutectic Mg2Si from rod or lamellae to
curved flake with larger eutectic spacing k, while increasing Si level promoted
the formation of rod-like or lamellar eutectic Mg2Si with smaller k.
• Mg addition shifts the eutectic point to lower Mg2Si concentration and
induces a slower eutectic growth rate, causing a lower Mg2Si volume fraction
in Al–Mg2Si eutectic cell.
• Si addition increased the Mg2Si volume fraction in eutectic cells by raising the
Mg2Si eutectic concentration and the eutectic growth rate.
• Formation of fine Al–Mg2Si eutectics, Si induced less ductility sacrifice than
Mg when achieving the same strength improvement.
Pseudo-binary diagram of Al–Mg2Si with extra 0%, 4% and 8% Mg. It was found
that excess Mg leads to three obvious changes:
(1) the solid solubility of Mg2Si in a-Al decreases remarkable;
(2) the Al– Mg2Si eutectic point moves towards lower Mg2Si concentration; and
(3) Al–Mg2Si eutectic reaction temperature range (TR Al–Mg2Si), namely the
temperature range of the three-phase region, becomes wider.
microstructures of Al–15%Mg2Si composites with different Be additions:
(a) 0.0 wt.%; (b) 0.1 wt.%; (c) 0.3 wt.%; and (d) 0.5 wt.%Be.
Effect of a Mg and b Si levels on the mechanical properties of die-cast Al–xMg 2.4Si
and Al–7.5Mg–xSi alloys.
Microstructure of Al-Mg2Si
 Al-Si-Mg alloy
• Al–Mg–Si alloys are widely used as medium-strength structural alloys which
have the additional advantages of good weldability, corrosion resistance, and
immunity to SCC.
• Magnesium and silicon are added in “balanced” amounts to form quasi-binary
Al–Mg2Si alloys (Mg:Si 1.73:1), or with an excess of silicon that needed to form
Mg2Si.
• Commercial alloys may be divided into three groups based on the strength
levels that may be attained in the T6 condition
• Balanced amounts of magnesium and silicon adding up to between 0.8% and
1.2%.
• Readily extruded and offer a further advantage in that they may be quenched at
the extrusion press.
• Moderate strength is developed by age hardening at 160–190°C.
 peak aged (T6) values of yield strength

• 6063, is perhaps the most widely used Al–Mg–Si alloys. In the T6 temper,
typical tensile properties are 0.2% proof stress 215 MPa and tensile strength
245 MPa.
• Al–Mg–Si alloys contain magnesium and silicon in excess of 1.4%. They develop
higher strength on ageing and, because they are more quench sensitive, it is
usually necessary to solution treat and water quench as separate operations
after extrusion.
• 6061 (Al–1Mg–0.6Si) to which is added 0.25% copper to improve mechanical
properties together with 0.2% chromium to offset any adverse effect coppe may
have on corrosion resistance.
• Contain silicon in excess of that needed to form Mg2Si and the presence of this
excess promotes an additional response to age hardening by both refining the
size of the Mg2Si particles and precipitating as silicon.
• Higher silicon contents may reduce ductility and cause intergranular
embrittlement ---segregate to the grain boundaries.
• Adding chromium (alloy 6151) and manganese (6351) helps to counter this effect
by promoting fine grain size and inhibiting recrystallization during solution
treatment.
• These alloys are used as extrusions and forgings. A more recent example of a
high silicon alloy is 6082 (Al–1Si– 0.9Mg–0.7Mn) which is a structural material.
• Actual atomic ratios Mg:Si in the intermediate precipitates that contribute
maximum age hardening in Al–Mg–Si alloys are close to 1:1 rather than the
expected 2:1 present in the equilibrium precipitate β (Mg2Si).
• Higher strengths may be achieved in Al–Mg–Si alloys by increasing the copper
content and the alloy 6013 (Al–1Mg–0.8Si–0.8Cu–0.35Mn) has a 0.2% proof
stress of 330 MPa for the T6 temper. 6061- 0.25Cu—YS- 275 Mpa.
• Alloys are hardened by the presence of the Q phase (Al5Cu2Mg8Si6) that
precipitates in addition to the phases which form in ternary Al–Mg–Si alloys.
• Al–Mg–Si alloys are normally aged at about 170°C and the complete
precipitation process is the most complex of all age-hardened aluminium alloys.
• Clustering of silicon atoms has been detected prior to the formation of GP
zones which can influence subsequent stages of precipitation.
Cast Al-Si-Mg Alloy
• Large quantities of sand and permanent mold castings are made from the Al–
Si–Mg alloys 356 or LM25 (Al–7Si–0.3Mg) and 357 (Al–7Si–0.5Mg) in which the
small additions of magnesium induce significant age hardening through
precipitation of phases that form in the Al–Mg–Si system.
• The yield strengths of these alloys in the T6 condition are more than double
that of the binary alloy containing same Si content.
• Relationships between microstructure and fracture characteristics is critical.
• Tensile fracture of Al–Si–Mg castings has been shown to initiate mainly by
cracking of eutectic silicon particles.
• 6xxx series alloys have good formability, weldability, machinability, and
corrosion resistance, with medium strength.

Relationships among commonly used alloys in the 6xxx series (Al-Mg-Si).

• Higher magnesium content of alloy 357 increases the response to age
hardening and higher tensile properties but disadvantage in that relatively
large particles of an intermetallic compound π (Al5Si6Mg8Fe2) may form.

Microstructure of alloy 357 showing relatively large π phase particles

 Al–Mn Phase diagram
• 10 at.%, with the (FCC)
Al-rich solid solution a
homogeneous
orthorhombic Al6 Mn.
• At 18 at. % of Mn,
growth of the Al6Mn
orthorhombic phase
with the β-Mn cubic
phase.
• Mn (41 at. %) , Al8Mn5 (γ2 ) and meta-stable ordered τ-AlMn phases are formed.
• τ-AlMn is generally produced from a massive transformation of the ε phase that
is usually observed at temperatures higher than 1073 K.
• formation of τ-AlMn depends on the annealing temperature and it decomposes
into β-Mn and Al8 Mn5 (γ2 ) after a long period of isothermal annealing.
 Al–Mn and Al–Mn–Mg alloys (3xxx series)
• The 3xxx series of alloys are used when moderate strength combined with
high ductility and excellent corrosion resistance is required.
• Commercial Al–Mn alloys contain up to 1.25% manganese although the
maximum solid solubility of this element in aluminium is as high as 1.82%.
• This limitation is due to the presence of iron as an impurity reduces the
solubility and there is a danger that large, primary particles of Al6Mn will
form with a disastrous effect on local ductility.
• The only widely used binary Al–Mn alloy is 3003 which is supplied as sheet as
it has good plasticity after cold working (under-cold rolling mill) and annealing
process.
• Finer manganese-containing intermetallic compounds confers some
dispersion hardening, and the tensile strength of annealed 3003 is typically
110 MPa compared with 90 MPa for CP aluminium.
• This alloy is commonly used for foil, cooking utensils, and roofing sheet.
• Addition of magnesium provides solid solution strengthening and the dilute
alloy 3105 (Al–0.55Mn–0.5Mg), is fabricated, is widely used in a variety of
strain hardened tempers.
• Higher levels of manganese and magnesium are present in 3104 (Al–1.1Mn–
1.05Mg–0.15Cu) which raises the tensile strength to 320 MPa in the H19
condition.
• This alloy is used for manufacturing beverage cans.
Linear
Thermal Modulus
Expansion Tensile Yield
Density Melting Conductiv of Elongatio
Alloy Coefficien Strength Strength
(g/cm³) Point (℃) ity Elasticity n (%)
t (10^- (MPa) (MPa)
(W/m·K) (GPa)
6/K)
3003 2.73 660 120 - 160 23.1 68 125 - 180 55 - 145 2 - 12

3004 2.72 640 - 660 120 - 160 23.6 73 180 - 230 70 - 190 1 - 10

3104 2.73 635 - 655 120 - 160 23.8 73 180 - 235 80 - 205 1 - 10

3105 2.73 635 - 655 120 - 160 23.8 73 180 - 230 80 - 210 1 - 10
microstructure of Al–Mn–Mg 3004 alloy
Al-Zn phase
diagram

• Solubility of Zn in Al is the largest among all elements, showing a maximum of

67at% at 654 K Zn and Al do not form intermetallic phases.
• At RT (298 K), the solubility of Zn in Al is 0.85 at%, and the one of Al in Zn is smaller
than 0.5 at%. atomic radius of Al is 0.143 nm, while the one of Zn is 0.134 nm.
Al-Zn phase diagram
• Alloy contains two phases: α-phase (fcc, the matrix, M) containing ≈ 99
at% Al and ≈ 1 at% Zn, and β-phase(hexagonal, the precipitates) having ≈
99.5 at% Zn and ≈ 0.5 at% Al.
• Alloys rapidly quenched from a temperature, Tt, higher than the solid-
solution temperature, Tss, to RT.
• When aged, at RT or at a higher temperature, these alloys decomposed,
and the precipitation of Guinier-Preston zones (GPZ) and β-phase, as
well as the transition of GPZ into the β-phase.
• During ageing, gradual transition of the α(M/GPZ)-phase, in a
metastable equilibrium with GPZ, to the α(M/β)-phase, in equilibrium
with the β precipitates.
• The slowly cooled alloys were much closer to the stable equilibrium
state, than the quenched and aged alloys.
• In the latter, the precipitates were not uniformly distributed in the
crystal lattice of the α(M/β)-phase, and residual strains in the α(M/β)-
phase around the β precipitates are present.
• During heating, microstructure changes like enhancing thermal
vibrations of atoms, thermal expansion, which was found anisotropic
for the β-phase, partial dissolution of the β-phase into the α(M/β)-
phase, a change of the shape of the β precipitates, phase transition of
the β-phase into the α'-phase, or the transition of both β- and α-phase
into the α'-phase, coexistence of the α'- and α-phases, or of the α'-, β-
and α-phases, a change of composition of particular phases, formation
of solid solution.
• Confirmed that the quenched-in vacancies, vacancy-Zn pairs and other
vacancy complexes play a dominant role in the diffusion rate of Zn.
• Defects in the crystal lattice of the α-phase, such as dislocations, grain boundaries, or
incoherent parts of the precipitate–α-phase interface, act as sinks (traps) for vacancies.
 Al–Zn–Mg alloys
• The Al–Zn–Mg system offers the greatest potential of all aluminium alloys
for age hardening.
• Medium-strength alloys containing little or no copper that have the
advantage of being readily weldable.
• These alloys differ from most other weldable aluminium alloys in that
they age harden significantly at room temperature.
• Weldable Al–Zn–Mg alloys were first developed for lightweight military
bridges and have other commercial applications.
• Many compositions are now available which may contain 3–7% zinc and
0.8–3% magnesium (Zn+ Mg in the range of 4.5–8.5%) together with
smaller amounts (0.1–0.3%) of one or more of the elements chromium,
manganese, and zirconium.
 M = MgZn2,

T = Al32(Mg,Zn)49

Section of ternary Al–Zn–Mg phase diagrams at 200°C.

• Elements are added mainly to control grain structure during fabrication
and heat treatment i.e. zirconium also improves weldability.
• Improvements in resistance to SCC have come through control of both
composition and heat treatment procedures.
• Zn+Mg content should be less than 6% in order for a weldable alloy to
have a satisfactory resistance to cracking.
• Maximum resistance to SCC occurs if the Zn: Mg ratio is between 2.7 and
2.9.
• Small amounts of copper and, more particularly, silver have been shown
to increase resistance to SCC.
• Changes in heat treatment procedures have led to a marked reduction in
susceptibility to SCC i.e. slower quench rates, e.g., air cooling, from the
solution treatment temperature which minimizes residual stresses and
decreases differences in electrode potentials throughout the
microstructure.
• Using 0.08–0.25% zirconium to replace chromium and manganese for
the inhibiting recrystallization because this element has the least effect
on quench sensitivity.
• zirconium forms small insoluble particles of Al3Zr whereas chromium
and manganese combine with some of the principal alloying elements to
form Al12Mg2Cr and Al20Cu2Mn3.
• 7xxx series alloys are used in airframe structures, mobile equipment, and
other highly stressed parts.
• Higher strength 7xxx alloys exhibit reduced resistance to stress corrosion
cracking and are often utilized in a slightly overaged temper to provide better
combinations of strength, corrosion resistance, and fracture toughness.

General relationship between resistance to SCC and strength during the ageing
Alloy Precipitates Remarks

Al–Zn–Mg GP zones; two types GP[1] Spherical, 1–1.5 nm, ordered.

GP [2] thin Zn disks, 1–2 atom layers thick,
form on {111}α. Partly ordered.
η′ (or M′) hexagonal May form from GP zones in alloys with
Zn:Mg > 3:1.
(0001)η′//(111)α; [1120]η′//[112]α. Semicoherent.
Disk-shaped. Composition close
to MgZn
η (or M) hexagonal Forms at or from η′, may have one of nine
MgZn2 orientation relationships with matrix. Most common
a = 0.521 nm are: (1010)//(001)α; (0001)η//
c = 0.860 nm (110)α and (0001)η//(111)α; (1010)//(110)α.
T′ hexagonal, probably Semi-coherent. May form instead of η in
Mg32 (Al, Zn)49 alloys with high Mg:Zn ratios.
a = 1.388 nm (0001)T′//(111)α; (1011)T//(112)α.
c = 2.752 nm
T cubic Mg32 (Al, Zn)49 May form from η if ageing temperature
a = 1.416 nm >190°C, or from T′ in alloy with high
Mg:Zn ratios.
(100)T//(111)α; [001]T//[112].
 S = Al2CuMg,
T = Al6CuMg4 + Al32(Mg,Zn)49,
M = MgZn2 + AlCuMg.

Section of Al–Zn–Mg–Cu phase diagram (1.5% Cu) at 460°C.

Hardness–time curves for the Al–Zn–Mg–Cu alloy 7075 aged at 130°C
and underaged 0.5 h at 130°C, quenched to 25°C, and held either at
this temperature or at 65°C.
 Al–Cu–Mg alloys (2xxx series)
• Alfred Wilm, working in Berlin in 1906, was seeking to develop a stronger
aluminium alloy to replace brass for the manufacture of cartridge cases for guns.
• Duralumin (Al–3.5Cu–0.5Mg–0.5Mn), which was quickly used for structural
members for Zeppelin airships.
• 2014 (Al–4.4Cu–0.5Mg–0.9Si–0.8Mn) in which higher strengths have been
achieved because the relatively high silicon content, increases the response to
hardening on artificial ageing.
• tensile properties are 0.2% proof stress 320 MPa and tensile strength 485 MPa.
• 2024, magnesium content is raised to 1.5% and the silicon content is reduced to
impurity levels, undergoes significant hardening by natural ageing frequently
used in T3 or T4 tempers.
• Also high response to artificial ageing.
• Microstructural features that influence toughness and ductility
• Equal values of yield strength, alloys in the 2xxx series have lower fracture
toughness than those of the 7xxx series (Al–Zn–Mg–Cu).
• Interrupted ageing treatments involving secondary precipitation have also
been found to increase fracture toughness in the Al–Cu–Mg alloy 2014.
• Increases in fracture toughness by using interrupted ageing treatments
were as follows: 2014 34.5%; 6061 58.6% and 17.4%; 7050 9.3%
• and 38.3%; 8090 28.1%; 357 2.0% and 38.8%.
Kinetics of precipitation
• The rate of precipitation is faster at higher temperature of aging.
• The rate of precipitation is faster in alloys of widely dissimilar metals.
• Impurities in soluble or in insoluble state invariably increase the rate of
precipitation.
• Plastic deformation, just before aging increases the rate of precipitation.
• The rate of precipitation is faster at a given aging temperature in a low
melting alloy than in a high melting alloy.
Rapid hardening phenomenon in Al–2.5Cu–1.5Mg and Al–2.5Cu–1.5Mg–0.5Ag alloys
during isothermal ageing at (A) 150°C and (B) 200°C.
• Addition of Ag Promotes formation of three new and quite different
precipitates depending on the Cu:Mg ratio
• Clusters of silver and magnesium form within seconds after artificial ageing
has commenced.
• Clusters have a loosely defined shape at the beginning, but gradually
evolve into nanoscale platelets during continued ageing.
• Copper atoms then quickly diffuse to the clusters leading to nucleation of
the precipitate Al2Cu.
Hardness–time curves for Al–4Cu and Al–4Cu–0.05In aged at 130°C and 190°C
 Microalloying effects
Nucleation and growth processes, some precipitation reactions may be greatly
influenced by the presence of minor amounts or traces of certain elements.
1. Preferential interaction with vacancies, which reduces the rate of nucleation of
GP zones.
2. Raising the GP zones solvus which alters the temperature ranges over which
phases are stable.
3. Stimulating nucleation of an existing precipitate by reducing the interfacial energy
between precipitate and matrix.
4. Stimulating nucleation of an existing precipitate by reducing the strain energy
between precipitate and matrix.
5. Promoting formation of a different precipitate.
6. Providing heterogeneous sites at which existing or new precipitates may nucleate.
7. Increasing supersaturation
 Hardening mechanisms

• Interference to slip by particles precipitating on crystallographic planes.

• Maximum hardening was associated with a critical particle size.
• strength of an age-hardened alloy is controlled by the interaction of
moving dislocations with precipitates.
• maximum hardening, is to be expected when the spacing between
particles is equal to the limiting radius of curvature of moving dislocation
lines.
• Coherent GP zones are, in fact, sheared by moving dislocations.
• Shearing of the zones increases the number of solute–solvent bonds
across the slip planes.
cutting of a fine particle, e.g.,
GP zone, by a moving
dislocation.

Shearing of fine precipitates

leading to planar slip and
dislocation pileups
at grain boundaries. (B) Stress
concentration at grain boundary
triple points due to
presence of PFZs.
Representation of a dislocation bypassing widely spaced particles
 Strengthening Mechanism
Solid Solutions Strengthening
➢ Impurity atoms distort the lattice & generate stress.
➢ Stress can produce a barrier to dislocation motion.
➢Strengthening effect increases as I△rI= rmatrix-rimp. Increases.
• Smaller substitutional • Larger substitutional
impurity impurity

C
A

D
B

Impurity generates local stress at C

Impurity generates local stress at A
and D that opposes dislocation
and B that opposes dislocation
motion to the right.
motion to the right.
• small impurities tend to concentrate
at dislocations on the “Compressive
stress side”
• reduce mobility of dislocation 
increase strength Stress Concentration at Dislocations

Adapted from Fig. 7.4,

Callister 7e.
• Large impurities concentrate at dislocations on
“Tensile Stress” side – pinning dislocation
 Reduce Grain Size

• Grain boundaries are

barriers to slip.
• Barrier "strength" increases
with increasing angle of
misorientation.
• Smaller grain size:
more barriers to slip.

• Hall-Petch Equation:

−1 / 2
 yield = o + k y d
Adapted from Fig. 7.14, Callister 7e.
(Fig. 7.14 is from A Textbook of Materials
Technology, by Van Vlack, Pearson Education,
Inc., Upper Saddle River, NJ.)
 Strain Hardening or Cold Work (%CW)
• Room temperature deformation.
• Common forming operations change the cross sectional area:

-Forging force -Rolling

roll
die Ad
A o blank Ad Ao
Adapted from Fig.
11.8, Callister 7e. roll

-Drawing force -Extrusion

Ao
die Ad container die holder
Ao tensile force
force ram billet extrusion Ad
die container die
Ao − Ad
%CW = x 100
Ao
 During Cold Work
• Ti alloy after cold working:
• Dislocations entangle and
multiply
• Thus, Dislocation motion
becomes more difficult.

Adapted from Fig.

4.6, Callister 7e.
0.9 mm (Fig. 4.6 is courtesy
of M.R. Plichta,
Michigan
Technological
University.)
Result of Cold Work
total dislocation length
Dislocation density =
unit volume
• Carefully grown single crystal
→ ca. 103 mm-2
• Deforming sample increases density
→ 109-1010 mm-2
• Heat treatment reduces density
→ 105-106 mm-2
Dislocation density increases, which leads to an increase in Yield
strength: Materials become harder. 
y1 large hardening
y0 small hardening

e
 Impact of Cold Work
As cold work is increased
• Yield strength (y) increases.
• Tensile strength (TS) increases.
• Ductility (%EL or %AR) decreases.

Lo-Carbon Steel!
Adapted from Fig. 7.20,
Callister 7e.
Cold Work Analysis
• What is the tensile strength &
ductility after cold working to 35.6%?

yield strength (MPa) tensile strength (MPa) ductility (%EL)

60
700 800

40
500 600
Cu
300 Cu 400 340MPa 20
Cu 7%
100 200
0 20 40 60 00
0 20 40 60 20 40 60
% Cold Work % Cold Work % Cold Work
YS = 300 MPa TS = 340MPa %EL = 7%

Adapted from Fig. 7.19, Callister 7e. (Fig. 7.19 is adapted from Metals Handbook: Properties and Selection: Iron
and Steels, Vol. 1, 9th ed., B. Bardes (Ed.), American Society for Metals, 1978, p. 226; and Metals Handbook:
Properties and Selection: Nonferrous Alloys and Pure Metals, Vol. 2, 9th ed., H. Baker (Managing Ed.), American
Society for Metals, 1979, p. 276 and 327.)
Effect of Heating After %CW
• 1 hour treatment at Tanneal...
decreases TS and increases %EL.
• Effects of cold work are reversed!

TR = recrystallization
TR temperature

Adapted from Fig. 7.22, Callister 7e. (Fig.

7.22 is adapted from G. Sachs and K.R. van
Horn, Practical Metallurgy, Applied Metallurgy,
and the Industrial Processing of Ferrous and
Nonferrous Metals and Alloys, American
Society for Metals, 1940, p. 139.)
Recrystallization Temperature, TR
TR = recrystallization temperature = point of highest
rate of property change
1. TR  0.3-0.6 Tm (K)
2. Due to diffusion → annealing time→ TR = f(t) shorter
annealing time => higher TR
3. Higher %CW => lower TR – strain hardening
4. Pure metals lower TR due to dislocation movements
• Easier to move in pure metals => lower TR
Annealing
•Process where material is heated to above the recrystallization
temperature of the sample and then cooled down.
•Main purpose is to improve Cold work properties by increasing
ductility and retaining most of the hardness.
•There are 3 steps involved with annealing: recovery, recrystallization
and grain growth.
Recovery
•During recovery, some of the stored internal strain energy is relieved
through dislocation motion due to enhanced atomic diffusion at the
elevated temperatures.
•Leads to reduction in the number of dislocations.
Recovery

Annihilation reduces dislocation density.

• Scenario 1 extra half-plane
of atoms Dislocations
Results from annihilate
diffusion atoms
and form
diffuse
a perfect
to regions
atomic
of tension
plane.
extra half-plane
of atoms
• Scenario 2
3. “Climbed” disl. can now tR
move on new slip plane
2. grey atoms leave by
4. opposite dislocations
vacancy diffusion
meet and annihilate
allowing disl. to “climb”
1. dislocation blocked; Obstacle dislocation
can’t move to the right
Recrystallization
• New grains are formed that:
-- have a low dislocation density
-- are small
-- consume cold-worked grains.
0.6 mm 0.6 mm

Adapted from
Fig. 7.21 (a),(b),
Callister 7e.
(Fig. 7.21 (a),(b)
are courtesy of
J.E. Burke,
General Electric
Company.)

33% cold New crystals

worked nucleate after
brass 3 sec. at 580C.
 Grain Growth
• At longer times, larger grains consume smaller ones.
• Why? Grain boundary area (and therefore energy)
is reduced.
0.6 mm 0.6 mm
Adapted from
Fig. 7.21 (d),(e),
Callister 7e.
(Fig. 7.21 (d),(e)
are courtesy of
J.E. Burke,
General Electric
Company.)

After 8 s, After 15 min,

580ºC 580ºC
coefficient dependent on
• Empirical Relation: material & Temp.
exponent typ. ~ 2
elapsed time
grain dia. At time t. d − d = Kt
n n
o

This is: Ostwald Ripening

Cold Worked grains. Initial Partial
Not annealed. recrystallization replacement of Complete
after 3 seconds @ grains, after 4 recrystallization
580˚C seconds after 8 seconds
©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning ™ is a trademark used herein under license.