Materials (1)

lecture 03 – Phases and properties

Dr. Janusz Bucki, PhD, MSEng, CEng

Wołoska 141, room 308, 02-507 Warszawa

janusz.bucki@pw.edu.pl

Warsaw, 2023/24
 Phases and structural constituents
in microstructure of an alloy
• Alloy is a metal composed of more than one chemical element.
• Phase – is chemically and structurally homogeneous portion of the material micro-
structure, separated from the rest of material by a boundary surface (phase boundary).
• Structural constituent - is a characteristic, metallographically discernible component of
the alloy microstructure. Can be a mixture of more than one phases

One-phased Multi-phased materials:

material spheroidal cast iron (left)
(Brass 70) and tool carbon steel (right)

grain boundary
perlite
(α + Fe3C) ferrite α perlite Fe C
different density of atoms in the plane of section graphite 3 2
(α + Fe3C)
Phases in alloys
• The phase can be formed by one or more chemical elements. The
phase formed by two or more elements which retains crystalline
structure of dominating chemical element, with other atoms
distributed in this crystalline structure is called a solid solution.
• To mark a solution Greek symbols are used (σ, β, τ, etc.).
• To mark pure element phases, their chemical symbols are used (Si, Fe,
etc.).
• Materials can contain one or more phases depend on their chemical
composition and temperature.
• The same phases can form different structural constituents.

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The Gibbs phase rule
relation between structure and the state variables
Phases of H2O
F=C–P+2
F – the number of degrees of freedom
C – the number of structural constituents (components)
P – the number of phases
• The state variables - (temperature, pressure, composition)
factors, that can be used to control the material structure
• The degrees of freedom - number of independent state variables
available for a system at equilibrium which can be changed
1538oC
without changing of the structure 1394oC
If pressure is treated as constant (which is very common in 912oC
engineering cases), it is ignored as a degree of freedom, so the rule
becomes:
Phases in pure iron
F=C–P+1
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 Equilibrium constitution of materials
(One component phase diagrams)
The relations between structure and
state variables are shown in phase Liquid Cooling of
Temperature pure iron
diagrams, which are the graphical Solid

representation of the Gibbs rule.

at fixed pressure:
F=C–P+1

Time 5
 Phases in two-component alloys
Binary phase diagrams
The lever rule
Microstructural
development L+S
during slow L
cooling
S
XL XA Xs
L + SS

Binary phase diagram ms

with complete solid mL

solution

XL2 XA XXL2
S2
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Binary phase diagram
with no solid solution

Eutectic phase diagram) Eutectic reaction:

Eutektos (greek) = easily Leut → A + B
melted

Hypereutectic
Hypoeutectic
composition
composition
Eutectic
composition
A A+B
Hypoeutectic B Hypereutectic
composition A+B composition 7
Eutectic phase diagram with limited solid
solutions

Liquid

Liquid

Liquid + β
Temperature

G H
(euthectic)

E’ 8
Eutectoid phase diagram with limited solid
solutions
Eutectoid – „eutectic like”

Eutectic reaction: Leutectic → γ + β

Eutectoid reaction: γeutectoid → α + β

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Binary phase
diagram with
four intermediate
compounds
Only this part of
diagram is needed
to analyze structure
of alloys in this
composition range

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Equilibrium state of the material
• The microstructure of the alloy at the
equilibrium state (for which its free energy is at
minimum under specified combination of the Metastable 1
temperature and pressure and composition) do
not change with time. Metastable 2
• Sometimes in solids the equilibrium state is not
completely achieved (the rate of approach to Stable
equilibrium is extremely slow) and such a
systems are in metastable state.
• Metastable states or structures may persist
practically forever, and they have big practical
significance (e.g., martensite and martensitic
structure in steels).
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Phase diagrams in practice
• The phase diagram (equilibrium diagram) summarizes the equilibrium
constitution of the alloy system when the alloy has no tendency for
changing the constitution with time.
• They give us the information about structure obtained at very slow
temperature changing.
• In practice, materials processing is rushed, and time becomes an
important factor. The temperature versus time history generate a
desired structure – such process(es) are called heat treatment.

If you feel you need some more detailed explanation of binary phase
diagrams try: youtu.be/h5dwpTqacqc (link rechecked 2022.10.23) 12
The complete structure of materials
The structure is determined by:
• the overall composition of alloy i.e. - the chemical elements and their
relative weights,
• the number of phases and their relative weights,
• the composition and crystalline structure (or lack of it) of each phase,
• geometrical information about phases and grains (shape, size and space
between them).
• mictrostructure – crystalline defects
The structure of the materials depends on the material composition (alloying elements and
their concentrations), the temperature and their technological treatment (time of heating,
rate of cooling, chemical and mechanical treatments).
There is a huge possibility to change the material mechanical properties (ultimate and yield
strength, plasticity, fracture toughness, etc.) just by changing of their microstructure. 13
 Crystallization

The influence of temperature on the speed of

crystallization

Equilibrium temperature of transformation

Growing rate
Temperature

Crystallization rate

Nucleation rate
Rate of process
Fine-grained materials are harder than coarse-grained one.
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The yield strength of steel can be tripled by decreasing their grain size by a ten-times.
 Structure of the solid castings

The top of ingot this line is cut off

1 - chill crystals
2 - columnar grains
3 - equiaxed grains
4 - contraction cavity

Casting defects:
• Contraction cavity
• Inhomogeneous grain size Revealed microstructure of small ingot
• Segregation of impurities https://www.phase-trans.msm.cam.ac.uk/2010/ingots.html
(growing columnar grain push impurities ahead from them and lead to band accessed 2020.11.01
of solid impurities e.g. sulfides in steel or gas bubbles from dissolved nitrogen ) 15
 Continuous casting

1 – Ladle (main tub)

2 2 – Tundish (intermediate tub)
3 – Water-cooled die (crystallizer)
Advantages: a – Liquid metal
b – Solid metal
• End very effectivelimination of
contraction cavities
3
• Reducing of segregations a
(because columnar grains are
smaller)
• Little work is needed to obtain a
b
finished section
• The process is highly automated

Radius – several meters to bend into

horizontal and straighten the hot rod

https://youtu.be/Hh32DtJs7dQ?t=30
Cutting to desired length - often 20 metres or more 16
 Dendritic solidification

https://youtu.be/mDSalwmICnU (see also https://youtu.be/wcsB0bOqa70) https://www.youtube.com/watch?v=S07fPo45BvM

(links checked 2022.10.23)

wojciechplonka.com (accessed 2021.10.07 – no longer available). Now (2022.10.23) at: https://www.facebook.com/wojtekplonkaphotography/

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 Twin boundary

Twins
Dendritic structure

Brass 70, after casting Brass 70, after 18

Brass 70, after annealing recrystallization annealing
Microstructure
of silumins
Hypoeutectic (<12.6wt.% Si) silumin
before and after
NaF (NaCl) modification

Temperature oC

wt% Si

Hypereutectic (>12.6wt.% Si) silumin

before and after
phosphorus modification

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 Microstructure of Fe-C alloys
Iron and its alloys:
• Armco iron (<0.02wt.%C)
• Carbon steels and cast steels (0.02 – 2.06wt.%C
• Cast irons (2.06 – 6.67wt.%C)

Steels Cast
irons
Perlite (0.8% C)

Eutectoid reaction at 723oC:

γ (0.8 wt.%C) → α (0.02 wt.%C) + Fe3C (6.67 wt.%C)

Cementite (6.67% C)
Ferrite (0.02% C)
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