Aleaciones y Diagramas de Fases

1.- poca
Mucha azúcar Conceptos: Fases,
azúcar
Componentes y
soluciones. Tipos de
Soluciones.
Solubilidad parcial.
Precipitación.

F = 1 C = 2 (azúcar y F = 2 C = 2 (azúcar y agua)

agua)alcohol etílico
↓

Concepto :
Solubilidad
Total
Concepto: Mismo
Esquema de un componente en 2 fases Concepto: Insolubilidad total
sistema de F = 2 C= 3 diversas . F =3, C= 3 F= 4 C= 4
 COMPONENTS AND PHASES
• Components:
The elements or compounds which are mixed initially
(e.g., Al and Cu)
• Phases:
The physically and chemically distinct material regions
that result (e.g., a and b).

Aluminum-
Copper
Alloy

Adapted from
Fig. 9.0,
Callister 3e.

3
Microestructura de una aleación Al-Cu

Al

Al + Al2Cu
Una aleación binaria (dos componentes) adoptará una de las
siguientes formas:

(a) Una solución sólida

(b) Dos componentes puros separados

(c) Dos soluciones sólidas separadas

(d) Un compuesto químico (estequiometría definida) junto a

una solución sólida

Para determinar en cuál de los 4 casos anteriores se

encuentra una aleación se estudia la microestructura
 Curva de enfriamiento de un elemento puro
en función del tiempo

Cuando comienza a
Temperatura

Líquido solidificar la
temperatura se
mantiene constante.
Líquido y sólido

Sólido

Tiempo
Curva de enfriamiento para una sustancia que posee
dos componentes o elementos y una dada
composición

Líquido A diferencia del caso

Temperatura

anterior el líquido y el
Líquido y sólido sólido coexisten no solo
a una temperatura sino
que en un rango de
Sólido temperaturas

Tiempo
 Temp Au (puro)

1064ºC

940ºC
Temp. constante

tiempo
Ag (pura)

Au Estructura FCC
Ag Estructura FCC T fusión= 1064
T fusión= 960 R at.= 1.74Å
R at.= 1.65Å
 Ag25Au75
Temp
Ag75Au25
1064ºC

Au Estructura F
T fusión= 10
R at.= 1.74Å

940ºC
Au (puro)

Ag (pura) tiempo

Ag Estructura FCC
T fusión= 960
R at.= 1.65Å
Ag50Au50
50% y 50%
(AgAu)
 Curva de enfriamiento para una sustancia que posee dos
componentes o elementos para diferentes composiciones el
elemento puro A tiene menor temperatura de fusión que el
elemento B

Elemento B puro curva

tiene una temperatura
de fusión

Elemento A puro curva tiene

una temperatura de fusión.
 Binary Phase Diagram
Melting
Liquidus point of B
Liquid
Temperature (L)

Melting
point of A Solidus
Solid Solution
(SS)

A B
wt% A  80 60 40 20 0
B mole fraction A
 Determination of phase(s) present
• Rule 1: If we know T and Co, then we know:
--how many phases and which phases are present.

• Examples:

Cu-Ni
phase
diagram

Melting points: Cu =
1085°C, Ni = 1453 °C

Solidus - Temperature where alloy is completely solid. Above this line, liquefaction begins.
Liquidus - Temperature where alloy is completely liquid. Below this line, solidification begins.
17
 Example: Reading a Phase Diagram

When an alloy is present

in a two-phase region, a
tie line at the
temperature of interest
fixes the composition of
T1 the two phases.

Say we want to find

composition, X1 at
temperature,T1:
CL = Composition of
Liquid at T1
CS = Composition of
X1 Solid solution at T1
 PHASE DIAGRAMS: composition of phases
• Rule 2: If we know T and Co, then we know:
--the composition of each phase.
Cu-Ni
• Examples:
system

Adapted from Fig. 9.2(b), Callister 6e.

(Fig. 9.2(b) is adapted from Phase Diagrams
of Binary Nickel Alloys, P. Nash (Ed.), ASM
International, Materials Park, OH, 1991.)

7
• (b) What is the composition of this liquid phase?
• Answer: The composition of this liquid phase corresponds to the
intersection with the (α + L)-L phase boundary, of a tie line constructed
across the α + L phase region at 1350°C, 59 wt% Ni;

Wt% Ni
20
PHASE DIAGRAMS: weight fractions of phases
• Rule 3: If we know T and Co, then we know:
--the amount of each phase (given in wt%).
• Examples:
Cu-Ni
system

S 43  35
WL     73wt %
R S 43  32
R
Wa   = 27wt% Adapted from Fig. 9.2(b), Callister 6e.
(Fig. 9.2(b) is adapted from Phase Diagrams
R S of Binary Nickel Alloys, P. Nash (Ed.), ASM
International, Materials Park, OH, 1991.)

8
• (c) At what temperature does complete melting of the alloy occur?
• Liquidus - Temperature where alloy is completely liquid. Below this line,
solidification begins.
• Answer: Complete melting of the alloy occurs at the intersection of this same
vertical line at 70 wt% Ni with the (α + L)-L phase boundary--i.e., about 1380°C;

Wt% Ni
22
• (d) What is the composition of the last solid remaining prior to complete melting?
• Answer: The composition of the last solid remaining prior to complete melting
corresponds to the intersection with α-(α + L) phase boundary, of the tie line
constructed across the α + L phase region at 1380°C--i.e., about 78 wt% Ni.

Wt% Ni
23
Change in structure on a phase diagram
The change in
structure of a
Cu-40% Ni alloy
during
equilibrium
solidification.
The nickel and
copper atoms
must diffuse
during cooling
in order to
satisfy the
phase program
and produce a
uniform
equilibrium
structure.
• Development of
microstructure
during the non-
equilibrium
solidification of a 35
wt% Ni-65 wt% Cu
alloy outcome:
• Segregation-
nonuniform
distribution of
elements within
grains.
• Weaker grain
boundaries if alloy is
reheated.
Cu 90 Ni 10
 MECHANICAL PROPERTIES: Cu-Ni System
• Effect of solid solution strengthening on:

--Tensile strength (TS) --Ductility (%EL,%AR)

Adapted from Fig. 9.5(a), Callister 6e. Adapted from Fig. 9.5(b), Callister 6e.

--Peak as a function of Co --Min. as a function of Co

12
 Binary Isomorphous Systems
Cu-Ni system:
• The liquid L is a homogeneous liquid solution composed of
Cu and Ni.
• The α phase is a substitutional solid solution consisting of
Cu and Ni atoms with an FCC crystal structure.
• At temperatures below 1080 C, Cu and Ni are mutually
soluble in each other in the solid state for all compositions.
• The complete solubility is explained by their FCC structure,
nearly identical atomic radii and electro-negativities, and
similar valences.
• The Cu-Ni system is termed isomorphous because of this
complete liquid and solid solubility of the 2 components.
28
• Heating a copper-nickel alloy of composition 70 wt% Ni-30 wt% Cu from
1300°C. At what temperature does the first liquid phase form?
• Solidus - Temperature where alloy is completely solid. Above this line,
liquefaction begins.
• Answer: The first liquid forms at the temperature where a vertical line
at this composition intersects the α-(α + L) phase boundary--i.e., about
1350°C;

Wt% Ni
29
 Example: Solution

• To identify a composition with a

liquidus temperature below
2600˚C, there must be less than
60 mol% MgO in the refractory.
• To identify a composition with
solidus temperature above
2300˚C, there must be at least 50
mol% MgO present.
• Consequently, we can use any
composition between 50 mol%
MgO and 60 mol% MgO. 50
Ejemplos de diagramas de fase de solubilidad total
Ejemplos de diagramas de fase de solubilidad total
 Importance of Phase Diagrams
• There is a strong correlation between
microstructure and mechanical properties, and
the development of alloy microstructure is
related to the characteristics of its phase
diagram.
• Phase diagrams provide valuable information
about melting, casting, crystallization and other
phenomena.

34
 Microstructure

• In metal alloys, microstructure is characterized

by the number of phases, their proportions,
and the way they are arranged.
• The microstructure depends on:
– Alloying elements
– Concentration
– Heat treatment (temperature, time, rate of cooling)

35
 SUMMARY

• Phase diagrams are useful tools to determine:

--the number and types of phases,
--the wt% of each phase,
--and the composition of each phase
for a given T and composition of the system.

• Alloying to produce a solid solution usually

--increases the tensile strength (TS)
--decreases the ductility.

26
 Summary
• Phase diagrams are useful tools to determine:
-- the number and types of phases present,
-- the composition of each phase,
-- and the weight fraction of each phase
For a given temperature and composition of the system.
• The microstructure of an alloy depends on
-- its composition, and
-- rate of cooling equilibrium

37
 Eutectic Diagram with No Solid Solution

• Another binary system with

components that are so
dissimilar that their solubility in
each other in nearly negligible.
• There exists a 2-phase region
for pure solids (A+B). Because A
and B cannot dissolve in each
other!
• The eutectic temperature
(eutektos greek for “easily
melted”) is the temperature
that eutectic composition is
fully melted.
 Eutectic
• A eutectic or eutectic mixture is a mixture of two or more
phases at a composition that has the lowest melting point.
• It is where the phases simultaneously crystallize from molten
solution.
• The proper ratios of phases to obtain a eutectic is identified
by the eutectic point on a binary phase diagram.
• The term comes from the Greek 'eutektos', meaning 'easily
melted.‘

39
Sistemas de dos componentes

Liquidus
Solidus

E= Eutéctico

Tres fases: A, B y líquido

Invariante

La solidificación de X dará cristales de A + B

en la proporción de la composición X
 Solidifcación
Sistemas de dos componentes
T1 99.9999 % Líquido 1
0.0001% Cristales A
T2
a/(a+b) *100 % Líquido 2
b/(a+b) *100 % Cristales A

T3
c/(c+d) *100 % Líquido 3
d/(c+d) *100 % Cristales A

TE
Comienza solidificación eutéctica
A temperatura constante
Two Component Eutectic Systems

T > T1 -- all liquid

T1 - TE -- liquid + A
at TE -- liquid + A + B
T < TE -- A + B all solid

T2
% crystals of A = b/(a + b) x 100
% liquid = a/(a + b) x 100

T3
% crystals of A = d/(d + c) x 100
% liquid = c/(c + d) x 100
Sistemas de dos componentes

Interpretación de Microestructuras
 Binary-Eutectic Systems
has a special composition
2 components with a min. melting T.
T(°C)
Cu-Ag system 1200
• 3 single phase regions L (liquid)
(L, a, b) 1000
• Limited solubility: a L+ a
800 779°C L+b b
a: mostly Cu T E 8.0 71.9 91.2
b: mostly Ag 600
• TE : No liquid below TE a  b
• CE : Composition at 400
temperature TE 200
0 20 40 60 CE 80 100
• Eutectic reaction C , wt% Ag
L(CE) a(CaE) + b(CbE)
cooling
L(71.9 wt% Ag) a(8.0 wt% Ag)  b(91.2 wt% Ag) 44
heating
Copper-Silver Phase Diagram
 Eutectic Reaction
• Solvus – (solid solubility line) BC, GH
• Solidus – AB, FG, BEG (eutectic isotherm)
• Liquidus – AEF
• Maximum solubility: α = 8.0 wt% Ag, β = 8.8 wt %Cu
• Invariant point (where 3 phases are in equilibrium) is at E; CE =
71.9 wt% Ag, TE = 779C (1434F).

• An isothermal, reversible reaction between two (or more) solid

phases during the heating of a system where a single liquid
phase is produced.
Eutectic reaction
L(CE) a(CaE) + b(CbE)

cooling
L(71.9 wt% Ag) a(8.0 wt% Ag)  b(91.2 wt% Ag)
heating 46
Microestructura eutéctica en Ag- Cu:

20 m

Ag (claro), Cu (oscuro)
 Composición eutéctica
Composición hipoeutéctica Composición hipereutéctica
 Pb-Sn Phase Diagram

Liquidus
Solidus
Solidus

Solidus

Solvus Solvus
 Solidification of Eutectic Mixtures
• Mixtures of some metals, such as copper & nickel, are completely soluble
in both liquid and solid states for all concentrations of both metals. Copper
& nickel have the same crystal structure (FCC) and have nearly the same
atomic radii. The solid formed by cooling can have any proportion of
copper & nickel. Such completely miscible mixtures of metals are called
isomorphous.

• By contrast, a mixture of lead & tin that is eutectic is only partially soluble
when in the solid state. Lead & tin have different crystal structures (FCC
versus BCT) and lead atoms are much larger. No more than 18.3 weight %
solid tin can dissolve in solid lead and no more than 2.2% of solid lead can
dissolve in solid tin (according to previous phase diagram).
• The solid lead-tin alloy consists of a mixture of two solid phases, one
consisting of a maximum of 18.3 wt% tin (the alpha phase) and one
consisting of a maximum of 2.2 wt% lead (the beta phase).

50
 (Ex 1) Pb-Sn Eutectic System
• For a 40 wt% Sn-60 wt% Pb alloy at 150°C, determine:
-- the phases present Pb-Sn
T(°C)
Answer: a + b system
-- the phase compositions
300
Answer: Ca = 11 wt% Sn L (liquid)
Cb = 99 wt% Sn
a L+ a
-- the relative amount 200 183°C L+b b
of each phase 18.3 61.9 97.8
Answer: 150
C - C0
W = b 100
a + b
a Cb - Ca
99 - 40 59
= = = 0.67
99 - 11 88 0 11 20 40 60 80 99100
Ca C0 Cb
W b = C0 - Ca C, wt% Sn
Cb - Ca
40 - 11 29
= = = 0.33 51
99 - 11 88
 (Ex 2) Pb-Sn Eutectic System
• For a 40 wt% Sn-60 wt% Pb alloy at 220°C, determine:
-- the phases present:
T(°C)
Answer: a + L
-- the phase compositions
300
Answer: Ca = 17 wt% Sn L (liquid)
CL = 46 wt% Sn L+a
-- the relative amount 220 a
200 L+b b
of each phase 183°C
Answer:
100
CL - C0 46 - 40 a + b
Wa = =
CL - Ca 46 - 17
6 0 17 20 40 46 60 80 100
= = 0.21 Ca C0 CL C, wt% Sn
29
C0 - Ca 23
WL = = = 0.79
CL - Ca 29 52
 EX: Pb-Sn EUTECTIC SYSTEM (2)
• For a 40wt%Sn-60wt%Pb alloy at 150C, find...
--the phases present: a + b Pb-Sn
--the compositions of system
the phases:
Ca = 11wt%Sn
Cb = 99wt%Sn
--the relative amounts
of each phase:

Adapted from Fig. 9.7,

Callister 6e. (Fig. 9.7 adapted
from Binary Phase Diagrams, 2nd ed., Vol. 3, T.B.
Massalski (Editor-in-Chief), ASM International,
Materials Park, OH, 1990.)
15
 Pb-Sn
• For lead & tin the eutectic composition is
61.9 wt% tin and the eutectic temperature is
183ºC -- which makes this mixture useful as
solder.
• At 183ºC, compositions of greater than
61.9 wt% tin result in precipitation of a tin-rich
solid in the liquid mixture, whereas
compositions of less than 61.9 wt% tin result
in precipitation of lead-rich solid.

54
 Microestructuras características en sistemas eutécticos

Callister
 Microestructuras características en sistemas eutécticos

Callister
Microestructuras características en sistemas eutécticos
(composición hipoeutéctica)
58
 Microstructures in Eutectic
Systems - IV Pb-Sn
• For alloys with18.3 wt% Sn < C0 < 61.9 wt% Sn system
• Result: a phase particles and a eutectic microconstituent

T(°C)
• Just above TE :
L: C0 wt% Sn
a L
L Ca = 18.3 wt% Sn
300 L CL = 61.9 wt% Sn
a
L+ a CL - C0
Wa = = 0.50
a CL - Ca
200 L+ b
TE b WL = (1- W a ) = 0.50
• Just below TE :
100 a+b Ca = 18.3 wt% Sn
Primary α
eutectic a Cb = 97.8 wt% Sn
eutectic b Cβ - C0
Wa =
Cβ - Ca = 0.727
0 20 40 60 80 100
18.3 61.9 97.8
C, wt% Sn Wb = 0.273 wt% Sn 59
Pb Sn plomo estaño
Microestructuras características en sistemas eutécticos
(composición eutéctica)
 Eutectic Phase Diagrams

Cooling curve for a eutectic a) Atom redistribution during

alloy is a simple thermal
arrest, since eutectics
freeze or melt at a single
temperature.
lamellar growth of a Pb-Sn
eutectic. Sn atoms from the
liquid preferentially diffuse to the
b plates, and Pb atoms diffuse to
the a plates. b) photograph of
the Pb-Sn eutectic.
 Lamellar Eutectic Structure
A 2-phase microstructure
resulting from the
solidification of a liquid
having the eutectic
composition where the
phases exist as a lamellae
that alternate with one Pb-rich
another.
Formation of eutectic Sn-rich
layered microstructure in
the Pb-Sn system during
solidification at the eutectic
composition. Compositions
of α and β phases are very
different. Solidification
involves redistribution of Pb
and Sn atoms by atomic
diffusion.
63
 Microstructures in Eutectic Systems - III

• Co = C E
• Results in a
eutectic
microstructure
with alternating
layers of a and
b crystals. Pb-Sn
system

cooling
L(61.9 wt% Sn) a (18.3 wt% Sn)  b (97.8 wt% Sn)
heating
 MICROSTRUCTURES
IN EUTECTIC SYSTEMS-III
• Co = CE
• Result: Eutecticmicrostructure
--alternating layers of a and b crystals.

Pb-Sn
system

Adapted from Fig. 9.12, Callister 6e.

(Fig. 9.12 from Metals Handbook, Vol.
9, 9th ed., Metallography and
Microstructures, American Society
for Metals, Materials Park, OH, 1985.)
Adapted from Fig. 9.11,
Callister 6e. 18
 Pb-Sn Microstructures

The dark layers are Pb-rich α

phase, the light layers are the Sn-
rich β phase.

66
 Strength of Eutectic Alloys
Interlamellar spacing
This is the distance between the center of one a lamella to the center of the
next a lamella.
A small interlamellar spacing indicates that the amount of a b interface area
is large.
A small interlamellar spacing therefore increases the strength of the eutectic.

The interlamellar spacing in a

eutectic microstructure.
 HYPOEUTECTIC & HYPEREUTECTIC

Adapted from Fig. 9.7,

Callister 6e. (Fig. 9.7
adapted from Binary
Phase Diagrams, 2nd
ed., Vol. 3, T.B. Massalski
(Editor-in-Chief), ASM
International, Materials
Park, OH, 1990.)

(Figs. 9.12 and

9.15 from Metals
Handbook, 9th ed.,
Vol. 9,
Metallography and
Microstructures,
American Society
for Metals,
Materials Park,
OH, 1985.)

Adapted from Adapted from Fig. 9.15,

Fig. 9.15, Callister 6e. Adapted from Fig. 9.12, Callister 6e. (Illustration
Callister 6e. only)
20
Lever Rule will give us the mass fractions or amounts of each phase

Wb=(Ca-Co)/(Cb -Ca)

Wa =(Co-Ca)/(Cb -Ca)

check: (Wb x Cb)+(Wa x Ca)= Co

Microestructura hipoeutéctica en Al-Cu

Al

Al + Al2Cu
Microestructura eutéctica en Al-Cu

Al + Al2Cu
Phase Diagram If Two Components
Form 3rd Compound
• Looks like two Eutectic Diagrams nextnewto each
compound
other. melts
congruently

Two Eutectic
Points

Compound Forms;
called line
compound
 Intermetallic Compounds

19 wt% Mg-81 wt% Pb

Mg2Pb

Note: intermetallic compounds exist as a line on the diagram - not a

phase region. The composition of a compound has a distinct chemical
73
formula.
 Eutectic, Eutectoid, & Peritectic
• Eutectic - liquid transforms to two solid phases
L cool a + b (For Pb-Sn, 183C, 61.9 wt% Sn)
heat

• Eutectoid – one solid phase transforms to two other solid phases

Solid1 ↔ Solid2 + Solid3
 cool a + Fe3C (For Fe-C, 727C, 0.76 wt% C)
heat

• Peritectic - liquid and one solid phase transform to a 2nd solid phase
Solid1 + Liquid ↔ Solid2
cool
 +L heat ε (For Cu-Zn, 598°C, 78.6 wt% Zn)

74
 Tipos de diagramas de fases
4. Peritéctico

Una reacción peritéctica es una reacción que involucra tres fases, tal que al
enfriar, dos fases (una de ellas líquida) se transforman en una única nueva
fase sólida

L(liq.) + α (sol) → β (sol).

Sistemas de dos componentes con solución sólida

Eutectoide Peritectoide

Tres fases sólidas están en equilibrio

Puntos invariantes con sólo fases sólidas
 Tipos de diagramas de fases

5. Peritectoide

Una reacción peritectoide es una reacción que involucra tres fases, tal que al
enfriar, dos fases sólidas se transforman en una única nueva fase sólida.

A + B → δ.
Sistemas de dos componentes con líquidos inmiscibles

M= Monotéctico
Josiah Willard Gibbs
• Josiah Willard Gibbs (1839 - 1903)
has been reckoned as one of the
greatest American scientists of the
19th century
• He provided a sound
thermodynamic foundation to much
of Physical Chemistry
• Yale educated, he was awarded the
first Doctor of Engineering in the
U.S., and was appointed Professor
of Mathematical Physics at Yale in
1871

81
 Cu-Zn System (Brass)

Cartridge brass:
70 wt% Cu
 Eutectoid & Peritectic
Peritectic transformation  + L 

Cu-Zn Phase diagram

Eutectoid transformation  +

86
 La microestructura de una aleación influye en sus propiedades

composición; tratamiento térmico y/o termomecánico

Forma de las fases

Escala de las fases
microestructura (esférica, tipo bastón,
(nm o μm or mm)
tipo placa, etc.)

microestructura

Propiedades
(mecánicas, eléctricas, etc.)