Phase diagrams

Fe-C binary system

Phase diagrams provide
some fundamental
knowledge of what the
equilibrium structure of
a metallic (or ceramic)
alloy is, as a function of
temperature and
composition.
 Pure substances: For pure substances, the idea of a phase is familiar:
ice, water and steam are the solid, liquid and gaseous states of pure
H2O – each is a distinct phase. A region of a material which has a
homogeneous atomic structure is called a phase. A phase can be
identified as a cluster of as few as 10 or so atoms, but it is usually
much more.

DEF. All parts of a material

with the same atomic
structure are a single phase.
Mixtures: Consider first a familiar example: a mixture of sugar and
tea. If the tea is hot enough, the sugar will dissolve completely. The
result is a solution of sugar in tea – a single phase. If the tea goes
cold, a sugary sediment develops. This has a distinct atomic structure
from the surrounding liquid, and so the cup now contains two separate
phases.
Processing of metallic alloys (which are mixtures of elements) leads to
microstructures in which the component elements are distributed in a
number of ways. In the liquid state for metals, more or less everything
dissolves completely, therefore forming a single phase.
 But in the solid state, things are more complex – for example, in a
binary alloy (i.e. a mixture of two components) the solid microstructure
usually takes one of three forms (examples later):

- A chemical compound (phase 1), with a

separated solid solution (phase 2).

Lamellar microstructure called pearlite,

consisting of the phases cementite(light)
Microstructure of a single-phase (alpha) and ferrite (dark).
copper-tin alloy.
Two separated solid solutions (two
A single solid solution (one phase). phases).
A solid solution is a solid in which one (or more) elements are
“dissolved" in another so that they are homogeneously dispersed, at an
atomic scale. Some solid solutions may be so dilute that they are
effectively the pure component. In the three types of solid
microstructures listed above, each solid solution or chemical compound
would be an identifiable phase.
A metallic alloy is a mixture of a metal with other metals or non-metals.
Ceramics too can be mixed to form ceramic alloys.

- Brass: a mixture of Copper (Cu) and Zinc (Zn).

- Carbon steel: based on Iron (Fe) and Carbon (C).
- Spinel: a ceramic alloy made of Magnesia (MgO) and Alumina (Al2O3).

The components s are the chemical elements that make up alloys.

Components are given capital letters: A, B, C or the element symbols Cu, Zn, C. In
brass the main components are Cu and Zn. In carbon steel the main components are
Fe and C.

A binary alloy contains two components. A ternary alloy contains three; a

quaternary alloy, four, etc.
Alloys are defined by their composition – i.e. the concentrations of the
components in weight % (wt%) or atom % (at %). The compositions of
phases, too, may be defined in weight % or atom %.

The constitution of an alloy is described by:

- The phases present;
- The weight fraction of each phase;
- The composition of each phase.
PURE MATERIALS
 SIMPLE BINARY SYSTEMS

Partition

Behavior
changes
adding
another
substance
.

(a) One-dimensional phase diagram for a pure substance: a temperature scale showing the
phase boundary between solid and liquid – the melting point; (b) the A-rich end of a binary A-
B phase diagram, illustrating partition of the melting point between solidus and liquidus
boundaries.
Isomorphous phase diagram for the Cu-Ni system.
“isomorphous” meaning “single-structured”
 COOLING CURVES
AND LATENT HEAT

Homework: What is the latent heat?

 THE SOLUBILITY LIMIT: SOLVUS BOUNDARIES

Solvus boundaries are the boundaries between the single and two-
phase regions.
 CONSTRUCTING A PHASE DIAGRAM WITH SOLUBILITY LIMITS
Partition

Partial phase diagram for the Pb-Sn system, showing the limiting behaviour at high
and low temperatures.
 CONSTRUCTING A PHASE DIAGRAM WITH SOLUBILITY LIMITS

field

Point of maximum solubility (highest satuation)

Partial phase diagram for the Pb-Sn system, showing the limiting behaviour at high
and low temperatures.
 CONSTRUCTING A PHASE DIAGRAM WITH SOLUBILITY LIMITS
Phase diagram for the Pb-Sn system, showing the limiting behaviour at high and low
temperatures.
At this special temperature and
composition, two solid phases and liquid of
that composition can co-exist.

DEF. The lower

limit of the
single-phase
liquid field
formed by the
intersection of
two liquidus
lines is called
the eutectic
point.
 Organ at St. Ouen
A. Cavaillé-Coll (1890)
In a single-
phase region,
phase and alloy
compositions
coincide. In a
two-phase
region the
phase
compositions lie
on the phase
boundaries at
either end of a
horizontal tie-
line through
the
constitution
point.
 Consider the following:
WSn = 20 wt% Sn at 250ºC

WLSn = 34 wt% Sn.

WSn = 12 wt% Sn
To find the weight fractions of the phases in any two-phase region (liquid-
solid, or two solid phases):

- Construct the tie-line through the constitution point;

- Read off the three compositions (for the alloy, and the two ends of the tie-
line);

- Apply the lever rule.

Many systems show intermediate phases: compounds which form
between components. Examples are CuAl2, Al3Ni and Fe3C. If the
components are both metallic, they are called intermetallic compounds.

Thermodynamically, compounds form because the particular

combination of components is able to form as a single phase with a
specific lattice having lower free energy than, say, a mixture of two
phases.

As a single phase of fixed composition, intermediate phases

have unique melting points (like pure components). The higher degree
of thermodynamic stability means that compounds often have higher
melting points.
The atomic % of components in a compound is called its stoichiometry.
Compounds are written in the form noted above, AxBy where x and y are
integers.

The at% of the components in an intermediate compound can easily be stated

by inspection, x/(x + y) and y/(x + y), e.g. Fe3C contains 25 at% C. In general
the integer values x and y are small, since the number of atoms that define
the repeating unit of the crystal lattice is also small. Compounds therefore
usually appear on phase diagrams with at% scales at simple integer ratios e.g.
25%, 33%, 50% and so on.

In principle they therefore plot as a vertical line representing the single phase
– with the compound then forming one of the phases in both of the two phase
fields to either side.
In principle they therefore plot as a vertical line representing the single phase
– with the compound then forming one of the phases in both of the two phase
fields to either side.
Features:
• It seems to has 5
One-phase field different phase
diagrams.
• Intermetallic compounds:
fixed composition. Do
not vary with T.
• Solidus lines are vertical.

Two-phase field
The iron-carbon system
 BCC

Austenita
FCC

Ferrite

One-dimension diagram Cooling curve

 Hierro α (alpha)
• Cristaliza hasta los 768°C
• Estructura cristalina BCC
• Distancia interatómica 2.86 Å
• Capacidad débil para formar
soluciones sólidas
• Baja disolución de carbono
• Es magnética (T < 768°C)
• Fase estable se llama Ferrita
 Hierro β (beta)
• Similar al Feα
• Se genera entre los 768°C y
900°C

• Distancia interatómica
• 2.9 Å a 800ºC
• 2.905 Å a 900ºC
• Estructura cristalina BCC
• No es magnética (T > 768°C)
• Mecánicamente tiene muy
poco interés.
 Hierro γ (gamma)
• Se forma entre los 900°C y
1400°C
• Estructura cristalina FCC
• Volumen mayor Feα (3.65 Å)
• Capacidad alta para formar
soluciones sólidas

• Disolución de carbono hasta

un 2%
• Hierro amagnético

• Fase estable se llama

Austenita
 Hierro δ (delta)
• Se forma entre los 1400°C y
1538°C
• Estructura cristalina BCC

• Reducción de la distancia
interatómica (2.93 Å)
• Máxima solubilidad de
carbono es 0.007% a 1487°C
• Poco interés en la siderurgia
• Se inicia la fusion Fe puro a los
1537°C
25 at% C
Ferrite, Austenite and δ-Iron Solid Solutions

A key characteristic of the iron-carbon system is the extent to which iron

dissolves carbon in interstitial solid solution, forming single phases. This is
where the changes between BCC and FCC are significant. The interstitial
holes are larger in FCC than in BCC. This leads to low solubility of carbon in
BCC ferrite and -iron, and much higher solubility in FCC austenite. Note that
the same names (ferrite, austenite and ) are applied equally to the
different states of pure iron and to the solid solutions they form with carbon.
The nomenclature “iron-rich solid (Fe)” is not much help to us, as there are
three distinct variants.
Eutectoid point

The lower limit of a single-

phase solid field formed by two
falling phase boundaries
intersecting in a “V” is called a
eutectoid point.
Eutectic point

The eutectic temperature coincides with the temperature of maximum

solubility of C in austenite, with falling solidus and liquidus lines enclosing
the two phase liquid + austenite region. Tie-lines in the other two-phase
regions indicate mixtures of the compound, iron carbide, with liquid and
austenite respectively.
 Fe-C Phase Diagram: Summary
Peritectic point
To summarise the key
nomenclature of the iron-carbon
system, the single phases are:

- Ferrite: α-iron (BCC) with up to

0.035 wt% C dissolved in solid
solution
- Austenite: γ-iron (FCC) with up
to 2.1 wt% C dissolved in solid
Two-phase solution
- δ-iron: (BCC) with up to 0.08
wt% C dissolved in solid solution
- Cementite: Fe3C, a compound
(iron carbide), with 6.7 wt% C.
The system has a eutectic point at
4.3 wt% C, a eutectoid point at 0.8
wt% C, and a peritectic point at
0.2 wt% C.
 Characteristics in the
Reaction name Equation
phase diagram
𝑐𝑜𝑜𝑙𝑖𝑛𝑔
Eutectic 𝐿 𝛼+𝛽

𝑐𝑜𝑜𝑙𝑖𝑛𝑔
Eutectoid 𝛼 𝛽+𝛾

𝑐𝑜𝑜𝑙𝑖𝑛𝑔
Peritectic 𝛼+𝐿 𝛽

Peritectoid 𝑐𝑜𝑜𝑙𝑖𝑛𝑔
𝛼+𝛽 𝛾

Monotectic 𝑐𝑜𝑜𝑙𝑖𝑛𝑔
𝐿1 𝛼 + 𝐿2
Eutectic

Eutectoid

Peritectic
CULTURAL PARENTHESIS

Microstructure: Each border of the cristal lattice is named grain boundary.

These boundaries are visible under microscope.

Hipoeutectoid iron

Cu-1.6%wt Be Alloy
Fase Ferrita
• Solución sólida del carbono Feα y Feβ
• Estructura cristalina BCC
• Baja solubilidad de carbono
• 0.008% a Tamb
• 0.022% a T = 723°C
• Características mecánicas
• Dúctil y maleable (alargamiento 35 a
40% )
• Baja dureza (90 HB)
• Resistencia a la rupture 275 MPa
• Magnética T < 768°C
• No magnética T > 768°C
Fase Austenita
• Solución sólida del carbono en Feγ
• Estructura cristalina FCC
• Alta solubilidad de carbono
• Hasta 2.11% T = 1130°C
• Características mecánicas
• Dúctil (alargamiento 30 a 60% )
• Alta dureza (300 HB)
• Resistencia a la rupture 860 a 1030
MPa
• Material paramagnético
• Estabilidad térmica
Fase Cementita
• Compuesto metaestable Fe3C con 6.67%
• Estructura ortorrombica
• 12 átomos Fe y 4 átomos de C
• 4.5 x 5 x 6.7 Å
• Alta solubilidad de carbono
• Hasta 2.11% T = 1130°C
• Características mecánicas
• Frágil (alargamiento < 5% )
• Alta dureza (68 HRC)
• Resistencia a la rupture 2.940 MPa
• Magnético T < 230°C
Fase Perlita
• Mezcla eutectoide
• 0.77% de C a Tconstante = 727°C)
• 88.6% Fe3C + 11.4% Feα
• Enfriamiento lento
• Tlímite = 727°C
• Características mecánicas
• Dúctil (alargamiento 15% )
• Media dureza (190 a 300 HB)
• Resistencia a la rupture 780 MPa
• Existen dos tipos:
• Pelita fina – Dura y resistente
• Perlita gruesa – Menos dura y más
dúctil
 Enfriamiento lento (perlita gruesa) Enfriamiento rápido (perlita fina)
Esfuerzo Resistencia Esfuerzo Resistencia
Carbono % de % de
de cedencia mecánica a la de cedencia mecánica a la
% elongación elongación
(psi) tension (psi) (psi) tension (psi)
0.20 42750 57200 36.5 50250 64000 36.0
0.40 51250 75250 30.0 54250 85500 28.0
0.60 54000 90750 25.0 61000 112500 18.0
0.80 54500 89250 23.0 76000 146500 11.0
0.95 55000 95250 13.0 72500 147000 9.5
Fase Ledeburita
• Naturaleza eutéctica
• Constituyente de las fundiciones
• Es estable en el rango 1148°C < T < 727°C
• No existe a temperatura ambiente
 Agujas en zig-zag
Fase Martensita
• Enfriamiento rápido de la austenita
• No ocurre la difusión del C
• Solución sólida sobresaturada de C en Feα
• Estructura tetragonal centrada
• Velocidad de enfriamiento alta (120°/h)
• Características mecánicas
• Frágil (alargamiento 0.5 a 2.5% )
• Alta dureza (48 a 68 HRC – 0.35 y 0.9 %C)
• Resistencia a la rupture 1.80 a 2.45 MPa
 Fase Bainita
• Constituyente intermedio entre Feγ y
martensita
• Tratamiento isotérmico Austempering (250 y
600°C)
• 500 y 550°C se obtiene bainita superior
• 250 y 400°C se obtiene bainita inferior
• Características mecánicas
• Frágil (alargamiento 5% )
Bainita inferior • Alta dureza (50 HRC – Promedio)
• Resistencia a la rupture 1.77 MPa
Bainita superior • Z = 46.4% (estricción relativa)
 Temperature (°C)

% wt A
It uses the standards from the American Iron and Steel Institute
(A.I.S.I.) and the Society of Automotive Engineers (S.A.E.). Alloy steels and
carbon steels for a number of years were designated with specific grades
by a four-digit SAE/AISE numerical index system. Grades for alloy steels
and carbon steels were identified by this system based on standard
chemical compositions. A discontinuity in the relationship between grade
designations and the AISI occurred as a result of the decision made by the
AISI to stop writing material specifications.

XXXX
Type of Amount of
material carbon in
selected. the steel.
Stainless steels are
also included in the
AISI steel
specifications range.
The stainless steels
are provided with
three digit numbers
starting with 2, 3, 4,
or 5. The 300 series
austenitic stainless
grades and the 400
series martensitic
grades are the
popular stainless
steel specifications.
Stainless steels are also included in the AISI steel specifications range.
The stainless steels are provided with three digit numbers starting with 2,
3, 4, or 5. The 300 series austenitic stainless grades and the 400 series
martensitic grades are the popular stainless steel specifications.

Four digit index classification

The first digit of AISI/SAE Steel Designation represents a general
category grouping of steels. This means that 1xxx groups within the SAE-
AISI system represent carbon steels.

Because of the variations in some of the fundamental properties among the

carbon steels, they are further divided into four classes.
Thus the plain carbon steels are
represented within the 10xx series
containing a maximum of 1.00% Mn.

Resulfurized carbon steels are

represented within the 11xx series.

Resulfurized and rephosphorized carbon

steels are represented within the 12xx
series.

Non-resulfurized high-manganese (up-to 1.65%) carbon steels are

represented in 15xx series. The non-resulfurized high-manganese
carbon steels are developed for ensuring better machinability.
The second digit of the series
indicates the presence
(concentration) of major
elements, which may affect
the properties of the steel.

Manganese Sulphur

Chromium Molybdenum

Nickel
The last two digits indicate that the carbon concentration is 0.01%.

For example:

steel

Major secondary
Non-modified carbon elements are not
steel present.
Additional letters added between the second and third digits
include B when boron is added (between 0.0005 and 0.003%) for enhanced
hardenability, and L when lead is added (between 0.15 and 0.35%) for
enhanced machinability. The prefix M is used to designate merchant
quality steel (the least restrictive quality descriptor for hot-rolled steel
bars used in noncritical parts of structures and machinery). The
prefix E (electric-furnace steel) and the suffix H (hardenability
requirements) are mainly applicable to alloy steels. The full series of
classification groups is shown in Table 2-4.

Boron Lead