Chapter 4 – Metals

Pivotal Questions:
- How do you work with metals?
- What advantages do alloys offer?
- What limitations do metals have?
- What happens to metals after their commercial
life?
Metals
 Most metals are found in nature as metal oxides
 Metal oxides are refined into pure metals using
chemical reducing agents through a process called
smelting
 Once the pure metal is formed, it is processed into
the desired shape via forming operations
 Forging
 Rolling
 Extrusion
 Drawing
Forging
 Forging is the manual reshaping of a metal by
hammering or pressing. The medieval blacksmith
pounding a horseshoe is a classic example, but the
mechanical pressing of metal blanks is a modern
industrial example

Forming Operations: Forging

Rolling
 Rolling is the thinning of a metal sheet by
compressing it between two rollers.
 Aluminum foil is made by rolling thick aluminum
ingots

Forming Operations: Rolling

Extrusion
 Extrusion is the pushing of a metal through a die that
results in the metal obtaining the shape of the hole
 It is directly analogous to the extrusion of polymers

Forming Operations: Extrusion

Drawing
 Drawing is similar to extrusion but the metal is pulled
through the die from below rather than being pushed
from above

Forming Operations: Drawing

Cold working (or strain hardening)
 Cold working is the
deformation of a material
above its yield strength that
results in significant plastic
deformation
 The yield strength of the
deformed metal increases to
the level of the applied stress,
but ductility is reduced.
 The stress-strain curve does
not change, but the load at
which plastic deformation
begins does
Loading-Unloading
Percent cold work
Annealing
 The changes to the mechanical properties and
microstructure of the metal during cold working can
be reversed through a thermal process called
annealing
 Annealing occurs in three stages:
 Recovery – large deformed grains form subgrains that
result in a reduction of the residual stresses
 Recrystallization – Small grains nucleate at subgrain
boundaries, resulting in a reduction in the number of
dislocations and a softening that results in the return of
the original mechanical properties
 Grain Growth – Small grains grow and consume
neighboring grains
Microstructural Impact of
Annealing

Recovery, Recrystallization,
and Grain Growth
Hot working
 The temperature at which recrystallization begins is
called the Recrystallization Temperature
 Hot Working is the deformation above the metal
above the recrystallization temperature and it results
in a very different microstructure
 During hot working, recrystallization occurs
continuously and the material can be plastically
deformed indefinitely
 No strengthening occurs and the metal remains
ductile
Alloys
 Alloys are homogeneous
mixtures of a metal with one
or more metals or non-
metals, often forming a solid
solution
 Careful selection of
compositions and processing
conditions allow for a wider
range of properties than
could be achieved by pure
metals alone
Phases and phase diagrams
 A phase is any part of a
system that is chemically and
physically homogeneous and
possesses a defined interface
with any adjacent phases
 Phases in most metals vary
with temperature and
composition
 Phase diagrams, like the one
shown on the right, provide a
wealth of information about
the equilibrium of phases
Binary Isomorphic Systems
 The simplest phase diagram
is for a binary isomorphic
system like the Nickel –
Copper system shown on the
right
 It is binary because only two
materials (nickel and copper)
are present
 It is isomorphic because there
is only one liquid phase (L)
and one solid phase (a)
present
 Interpreting a phase diagram
 Consider a 50% mixture of
copper and nickel
 A single metallic phase (a) will
exist at all temperatures below
about 2300°F
 Between 2300°F and 2400°F, a
liquid phase exists in
equilibrium with solid a
 Just above 2400°F, the last solid
melts and a single liquid phase
(L) exists
 The upper line above which only
liquid exists is called the
liquidus line
 The lower line below which only
solids exist is called the solidus
line
Determining compositions
 Consider a system with 50%
nickel at 1290°F
 Although the total nickel
composition is 50%, the
amounts in the solid and
liquid phases will be
different.
 The composition of each
phase can be found be
constructing a horizontal like
(called a tie line) connecting
the regions of interest
Determining compositions (cont.)
 The intersection of the tie
line and the equilibrium
curve provides the
compositions of each phase
 The tie line intersects the
liquidus line at 43% nickel
indicating that the liquid
phase contains 43% nickel
 The tie line intersects the
solidus line at 56% nickel so
the solid phase (a) contains
56% nickel
Mass balances
A total mass balance and species mass balance will
determine the total amount of material in each phase.
Ma + ML = MT (Total mass balance)
wa Ma + wL ML = wTMT (species mass balance)

Where M is mass
w is weight percent
T indicates total
a indicates the amount in the a-phase
L indicates the amount in the L-phase
The lever rule
 Although mass balances work
to solve every problem, some
people prefer to use the lever
rule
 The same tie line is broken
into two segments (A and B
as shown)
 With a basis of 1 gram of
material, the mass of each
phase can be calculated from
Ma=B/(A+B) and ML = A/(A+B)
Diffusion in solids
 Phase diagrams represent an equilibrium state, but
time is required for the atoms to realign
 Concentration gradients drive the movement of atoms
from regions of higher concentration to those of lower
through a process called diffusion
 Diffusion in solid occurs the same way as diffusion in
liquids or gases, but at much slower rates
Fick’s First Law of Diffusion
 For steady-state systems, Fick’s First law provides

where JA is the net flux (atoms /area-time) of molecules

of material A moving in the x-direction because of a
concentration gradient (dCA/dx)
The term DAB is the diffusivity and represents how easily
an atom of material A can diffuse through material B
Factors that impact diffusion
 Diffusion is a strong function of temperature. Higher
temperatures indicate more molecular movement and
easier diffusion
 Crystal structure impacts diffusion. For example,
carbon will diffuse more easily in a BCC structure than
an FCC structure
 The mechanism of diffusion also matters
 Interstitial diffusion is the movement of an atom from
one interstitial site to another without disrupting the
lattice
 Vacancy diffusion is the movement of an atom into a
vacant site, leaving a new vacancy behind
Interstitial diffusion

Interstitial Diffusion
Vacancy Diffusion

Vacancy Diffusion
Time dependence
 Fick’s second law of diffusion
defines the time dependence of
diffusion but the solution of the
resultant partial differential
equation is beyond the scope of
this text
 However, time dependence does
impact microstructures
 Consider the cooling shown at
the right, the first solid formed
(at A) will have less nickel than
the solid formed at point B,
which well have less than point
C
Segregation
 Thus, the first layer to form
(the inner layer) will have
much less nickel than the
outer layers, which will
impact the properties of the
metal

 This phenomenon is called

segregation

Lighter colors indicate less

nickel
Segregation
Binary Eutectic Systems
 The next level of complexity
in phase diagrams is the
binary eutectic system, like
the lead-tin system shown at
the right
 Binary again signifies two
components
 Eutectic comes from the
Greek for “good melting” and
has a point at which the solid
phases melt directly to a
single liquid phase
Eutectic Isotherms
 Binary eutectics contain six
distinct regions: one single
phase liquid (L), two single
phase solid regions (a and b),
and three multiphase regions
(a + L, b + L, and a + b)
 The defining feature is a
horizontal eutectic isotherm
that represents the portion of
the solidus line above the a +
b solid solution
 In the lead-tin system, the
eutectic isotherm is at 183°C
The Eutectic Reaction
 The point on the eutectic
isotherm where the a + b
solid solution melts directly
to liquid is called the
eutectic point
 The eutectic point occurs at
the eutectic temperature (TE)
and eutectic composition
(CE)
 A Euctectic Reaction occurs
at the eutectic point
L(CE) <--> a(Ca,E) + b(Cb,E)
or for lead-tin
L(61.9%Sn) <--> a(18.9%Sn) +
b(97.8% Sn)
Solvus lines
 Binary eutectics also have
lines that separate pure phase
solids from mixed phase
solids.
 These lines are called solvus
lines
 The solvus lines for the lead-
tin system to the right are
indicated in red
Invariant points
 The eutectic is just one type of Invariant point each
with a characteristic reaction
Eutectoids
 Eutectoids are invariant points at which one solid
phase is in equilibrium with two different solid phases
Peritectics
 Peritectics are invariant points in which a solid and
liquid phase are in equilibrium with a different solid
phase
Carbon Steel
 Steel is the most common metal
used in industrial societies
 It is an alloy of interstitial
carbon atoms in an iron matrix
 Steel is produced from three
basic raw materials – iron ore,
coal, and limestone
 Iron ore is blended with coke
(coal with the volatiles removed)
in a blast furnace
 Limestone forms a slag to
remove impurities
 Iron ore is reduced to iron and
oxygen is added to remove
excess carbon
The steel phase diagram
 Like any other phase diagram,
the carbon composition could
extend from 0 to 100%
 However, the maximum
carbon percentage in steel is
6.7%
 Above 6.7%, iron carbide
(Fe3C) precipitates out of the
solid solution in a hard,
brittle phase called cementite
 As a result, the steel phase
diagram is essentially an iron
– iron carbide phase diagram
The steel phase diagram (cont.)
 The extreme lower left
consists of a BCC a-ferrite
phase. The solubility of
carbon in BCC is low (0.02%)
 The bulk of the low
temperature regions consists
of a two phase mixture of a-
ferrite and cementite that is
called Pearlite, because its
color resembles the mother-
of-pearl color common in
oyster shells
 Pearlite Microstructure
 The microstructure of
pearlite consists of
alternating layers of
cementite and a-ferrite.

 The thickness of these layers

is determined by processing
conditions
Steel Phase Diagram (cont.)
 The d-ferrite phase in the
upper left is a BCC phase that
is similar to a-ferrite but with
higher carbon solubility
(0.09%)
 Between the two ferrite
phases is an FCC phase called
austenite (g) with a much
higher carbon solubility (up
to 2.08%)
Austenite Microstructure
 Austenite exists only between
727°C and 1493°C

 The microstructure is shown

on the right

 Most steel phase transitions

start with the conversion to
austenite
Steel Invariant Points
 The steel phase diagram
contains three distinct
invariant points:
 A eutectoid at 723°C and
0.76% carbon
 A eutectic at 1147°C and
4.30% carbon
 A peritectic at 1493°C and
0.53% carbon
The steel eutectoid reaction
 The eutectoid reaction for steel can be written as

g (0.76%C) <--> a (0.022%C) + Fe3C (6.67%C)

 Steel with exactly 0.76wt% carbon is called eutectoid

steel
 Steel with carbon percentages above 0.76wt% is called
hypereutectoid steel
 Steel with carbon percentages below 0.76wt% is called
hypoeutectoid steel
Non-Equilibrium Products
 When austenite cools, the phase diagram indicates that pearlite
will form, but the transformation requires significant time for
the FCC lattice to convert to the BCC ferrite lattice
 If the material cools rapidly, non-equilibrium products form
with different properties
 Five non-equilibrium products:
 Martensite
 Bainite
 Spheroidite
 Coarse Pearlite
 Fine Pearlite
Martensite
 Product of the diffusionless
transformation of austenite.
 All carbon atoms remain as
interstitial impurities in the
iron lattice
 Requires immediate
quenching
 Harder and stronger than any
other carbon steel product,
but less ductile
 Microstructure consists of
elongated BCC cells
Martensitic Transformation
 The diffusionless martensitic
transformation is not limited
to steel. The ability to
undergo such a
transformation is called
hardenability
 Hardenability is measured by
the Jominy Quench Test
 A heated test specimen is
quenched rapidly by a spray
of water. The depth of
increased hardness is
measured
Bainite
 Produced by cooling rapidly
to between 550°C to 250°C
and allowed to remain at that
temperature
 Bainite is a ferrite matrix with
elongated cementite particles
 The microstructure shows a
distinctive needle-like
pattern
 Falls between martensite and
pearlite in terms of strength,
hardness, and ductility
Spheroidite
 Spheroidite is produced by
heating bainite or pearlite to just
below the eutectoid temperature
for 18 to 24 hours
 Cementite particles transform
into small spheres suspended in
an a-ferrite matrix
 Product is much less hard and
strong than pearlite, but is far
more ductile
Coarse vs Fine Pearlite
 Coarse pearlite consists of thick alternating layers of
cementite and pearlite and forms from treatments just
below the eutectoid temperature
 Fine pearlite has thinner alternating layers because it
is produced at lower temperatures and the diffusion
rate slows
 Coarse Pearlite is less strong and hard than fine
pearlite, but is more ductile
Summary of Non-Equilibrium
Products
Alloy Steels
 Steels may have other elements than just carbon and
iron
 Alloy steels contain up to 50% of nonferrous elements
that provide different properties
 Steel with at least 12% chromium is called stainless
steel
 Most of the chromium dissolve into the lattice while
the rest forms carbide precipitates
 The chromium converts the lattice to a chromium-iron
binary alloy that remains in its BCC shape and is far
more stable than a regular iron lattice
Types of stainless steels
 Ferritic stainless steels contain chromium without
nickel and are less expensive than those containing
nickel
 Martensitic stainless steels have 12-17% chromium
added to steel containing 0.15% to 1% carbon and can
undergo the martensitic transformation. They are
stronger than other stainless steels, but less corrosion
resistant
 Austenitic stainless steels have 7% - 20% nickel that
help maintain an FCC structure even when the steel is
cooled to ambient temperature. The steel is more
malleable and far more corrosion resistant
AISI/SAE Designation for steel
Phase transformations
 All of the phase transformations require time
 Small nuclei of the new phase form and must remain
stable long enough to grow
 As the new phase grows, the parent phase is consumed

Phase Transformation
And Grain Growth
The Avrami Equation
 The Avrami equation is used to evaluate the fraction of
material (y) converted to a new phase as a function of
time
y = 1 – exp (-ktn)
k and n are constants for a given material at a
given temperature
 The rate of transformation follows the Arrhenius
equation
r = Q0exp(-EA/RT)

where Q0 is a material-specific constant, EA is the activation

Transformation curves
 For most metals, a curve comparing fractional
conversion to the logarithm of time can be constructed
to show the time spent in nucleation and the onset of
grain growth
 Unfortunately, the plot is only valid at one temperature
Transformations at various
temperatures
 A series of curves at different
temperatures is needed to
characterize the conversion at
different temperatures

 These curves provide much

information, but are
cumbersome to use in
practice
Isothermal transformation
diagrams (T-T-T Plots)
 The information from many such curves are combined
in an isothermal transformation diagram
Key parts of T-T-T plots
 Begin curves represent the onset of the first
conversion to the new phase
 50% completion curves show the how much time is
required to convert half of the parent phase
 Completion curves show how much time is required
to finish the entire transformation
Continuous Cooling Curves
 Continuous cooling curves
(like the one on the right) are
used to characterize phase
changes associated with
cooling at a constant rate
 The curve representing the
critical cooling rate is the
most important
 Any rate slower than this, the
martensitic transformation
cannot occur
Age hardening (or precipitation
hardening)
 Process uses changes in solubility with temperature to
foster the precipitation of fine particles of impurities
 The particles serve as barriers to the propagations of
dislocations through the matrix, so they strengthen
the metal
 The process occurs in two stages
 Solution heat treatment
 Precipitation heat treatment
Solution heat treatment
 Metal is heated and held above the solvus line until
one phase dissolves completely in the other (to point
T1)
 The alloy is cooled to room temperature (T0) creating a
supersaturated solution of b dissolved in a
Precipitation Heat Treatment
 The metal is reheated but below the solvus line (to T2)
 At this temperature the b-phase forms a fine
precipitate
Copper and its alloys
 Main copper ores are
chalcocite (Cu2S) and
chalcopyrite (CuFeS2)
 Pure copper has a distinctive
red color and a green patina
when oxidized (like the
Statue of Liberty)
 It is highly conductive and
used in electronic wires, but
is toxic so copper cookware is
lined with stainless steel or
tin
Commercial Copper
 Low alloy coppers contain up to 5% of other metals
(commonly cadmium) to increase the strength and
hardness
 Copper can form 82 different binary alloys
 The two most common are brass (copper-zinc) and
bronze (copper-tin)
Brass
 Below 35% zinc, brass exists
as a single-phase with the
zinc atoms in solution in the
copper lattice
 Increasing zinc content
strengthens the metal but
reduces corrosion resistance
 Above 35% zinc, a BCC b-
phase dominates and the a-
phase precipitates out
Widmanstatten Structure
 The resultant microstructure
(shown at the right) consists
of b-grains surrounded by the
a-precipitate
 The structure is named after
Count Alois von Beckh
Widmenstatten who
discovered it in a meteorite in
1908
Other properties of brasses
 Brasses are lustrous, corrosion-resistant, and easily
cast which makes them ideal for decorative figures and
architectural trim
 They also find use in plumbing fixtures, piping, and
gears
 Lead (up to 4%) is often added to improve
machinability and to fill pore spaces in the metal
Bronze
 First appeared in Sumatra in
3500 B.C.
 Bronze is harder than most
commercial alloys, corrosion
resistant, and easily cast
 Most bronzes contain about
10% tin
 Bronze makes exceptional
casts because the metal
shrinks slightly, making it
easy to remove from the mold
while maintaining the shape
Other additives to bronze
 Silicon (added between 1-3%) makes the bronze
harder to cast but significantly improves its chemical
resistance
 Lead bronzes (up to 10% lead) are softer, easier to
shape, and better able to hold a cutting edge. They are
often used in artistic castings, but not in tools because
the metal becomes less strong and more brittle
 Antimony is added to bronze used for tools because it
hardens the material and helps it hold a cutting edge
Aluminum and its alloys
 Aluminum is the most abundant metallic element on
earth
 Its density is approximately 1/3 that of steel
 Nearly all aluminum is produced from bauxite ore
 Aluminum is used extensively in aerospace, cars,
beverage cans, and packaging
 Aluminum alloys are classified as either wrought
(shaped by plastic deformation) or cast (poured into a
mold)
Aluminum nomenclature
 Much like steel, a standard
nomenclature exists to
identify the composition of
the alloy

 Cast alloys have an decimal

added to distinguish them
from wrought alloys
Temper designations
 Aluminum alloys also have an alphanumeric
supplement to show whether it has been heat treated
(T) or strain hardened (H)
Corrosion
 Corrosion is the loss of material because of a
chemical reaction with the environment. To
understand corrosion, one must recall
electrochemistry

 The key is the oxidation reaction in which metals

transfer electrons to another material. The oxidation
reaction occurs at the anode and can be represented as

Metal -> Metal ion(n+) + n-lost electrons

Reduction
 The lost electrons must be picked up by another
species in a reduction reaction occurring at the
cathode. It can be represented as
Metal ion(n+) + n-lost electrons -> Metal
 The total number of electrons cannot change so the
oxidation and reduction occur at the same time
Electrochemical Cell
 Two solutions (in this case tin
and copper) are separated by
an insulator
 A piece of tin is place in the
tin solution and connected by
a wire to a piece of copper in
the copper solution
 Electrons flow from the tin to
the copper causing the tin to
corrode and the copper to
plate on the surface.
 The process is called
electroplating
Electrochemical Cell
The Galvanic Series
 The Galvanic series ranks
metals in order of their
likelihood to oxidize when
connected to other metals in
solution with their ions
 The table provides crucial
information about which
metal will behave as the
cathode and which will
behave as the anode
Passivation
 The Galvanic series differentiates between passive and
active forms of some alloys
 Passive alloys have become less anodic because of the
formation of a thin oxide barrier the hinders the
diffusion of oxygen
 The spontaneous formation of the protective barrier is
called passivation
Types of corrosion
 There are eight distinct forms of corrosion
 Uniform attack
 Galvanic corrosion
 Pitting
 Crevice corrosion
 Intergranular corrosion
 Stress corrosion
 Erosion corrosion
 Selective leaching
Uniform attack and galvanic
corrosion
 Uniform attack – the most common form of corrosion
in which the entire metal surface is electrochemically
attacked and a residue is left behind. Protective
coatings are used to resist uniform attack
 Galvanic corrosion – when metals are connected, the
metal that is lower on the galvanic series will oxidize in
favor of the more cathodic metal. Selecting metals
close to each other on the galvanic scale reduces the
problem
Pitting and crevice corrosion
 Pitting – corrosion that results from corrosive
materials gathering in small holes or scratches on the
metal surface. The corrosive material oxidizes the
metal in the hole, creating a deeper pit and ultimately
perforating the metal. Stainless steel with at least 2%
molybdenum resist pitting
 Crevice corrosion – is similar to pitting and occurs
where stagnant films of corrosive materials exist (like
the underside of bolts, rivets, and gaskets. Crevice
corrosion is reduced by using welds instead of rivets
and teflon gaskets.
Intergranular corrosion
 Intergranular corrosion occurs at grain boundaries
that are more susceptible than the main lattice.
Materials with precipitated phases are particularly
susceptible
Stress and erosion corrosion
 Stress corrosion results from the combined effects of a
corrosive environment and a tensile stress. Stress
corrosion is a highly material specific phenomenon
and such materials often experience brittle failure even
though they are naturally ductile
 Erosion corrosion results from mechanical abrasion of
a metal by a corrosive material. Passive metals are
particularly susceptible because the erosion wears
away the protective barrier
Selective leaching
 Selective leaching refers to the preferential elimination
of one constituent of a metal alloy. The metal lower on
the galvanic series remains in solution while the more
cathodic material is replated. The result is a lattice
deficient in the less cathodic material.
Recycling of Metals
 Metals are the easiest material to recycle
 Nearly 50% of all metal in the U.S. is recycled.
 Metal for recycling is called scrap metal
 Scrap coming from preconsumer sources is called new
scrap while that coming from consumer products is
called old scrap