Diagramas de fase

Profesora: Dra. Marcela Nohemí Ibarra Castro

 Phase Diagrams
• System: a portion of the universe that has
been isolated so that its properties can be
studied.
• Equilibrium: a system is said to be in
equilibrium if no macroscopic changes
take place with time.
• Phase: a physically homogeneous and
distinct portion of a material system.
• Equilibrium phase diagram: a graphical
representation of the pressures,
temperatures, and compositions for which
various phases are stable at equilibrium.
In materials science the most common
phase diagrams involve temperature
versus composition.
Phase Diagrams
A phase diagram shows the conditions at which the distinct phases of
matter can occur at equilibrium.
 Gibbs phase rule
➢The
. statement that at equilibrium the
number of phases plus the degrees of
freedom equals the number of
components plus 2.
➢Degrees of freedom F: the number of
variables (temperature, pressure, and
composition) that can be changed
independently without changing the
phase or phases of the system.
➢Number of components of a phase
diagram: the number of elements or
compounds that make up the phase-
diagram system. For example, the Fe-
Fe3C system is a two-component
system; the Fe-Ni system is also a two-
component system.
 2+C=F+P
A

X
Solid Solution
When in a solid, the atoms of solute are present in tha latttice of
solvent, it is known as solid solution.
Hume-Rothery rules
The Hume-Rothery rules, named after William Hume-Rothery, are a
set of basic rules that describe the conditions under which an
element could dissolve in a metal, forming a solid solution.
Substitutional solid
solution rules
For substitutional solid solutions, the Hume-Rothery rules are follows:
✓The atomic radius of the solute and solvent atoms must differ by no
more than 15%
✓The crystal structures of solute and solvent must be similar.
✓Complete solubility occurs when the solvent and solute have the
same valency. A metal of higher valency is more likely to dissolve in
a metal with lower valency.
✓The solute and solvent should have similar electronegativity. If the
electronegativity difference is too great, the metals tend to
form intermetallic compounds instead of solid solutions.
Interstitial solid
solution rules
For interstitial solid solutions, the Hume-Rothery rules are:
✓Solute atoms must be smaller than the interstitial sites in
the solvent lattice.
✓The solute and solvent should have
similar electronegativity.
✓They should show a wide range of composition.
✓Valency factor: two elements should have the same
valence. The greater the difference in valence between
solute and solvent atoms, the lower the solubility.
SOLUBILITY LIMIT
For many alloy systems and at some specific
temperature, there is a maximum concentration of
solute atoms that may dissolve in the solvent to form
a solid solution; this is called a solubility limit.
The addition of solute in excess of this solubility limit
results in the formation of another solid solution or
compound that has a distinctly different composition.
BINARY ISOMORPHOUS SYSTEMS
➢Possibly the easiest type of binary phase
diagram to understand and interpret is
that which is characterized by the
copper–nickel system.
➢The composition ranges from 0 wt% Ni
(100 wt% Cu) on the left horizontal
extremity to 100 wt% Ni (0 wt% Cu) on
the right.
➢Three different phase regions, or fields,
appear on the diagram, an alpha (α) field,
a liquid (L) field, and a two-phase α + L
field.
➢Each region is defined by the phase or
phases that exist over the range of
temperatures and compositions delimited
by the phase boundary lines.
➢The liquid L is a homogeneous liquid
solution composed of both copper and
nickel.
➢The phase α is a substitutional solid
solution consisting of both Cu and Ni
atoms, and having an FCC crystal
structure.
➢At temperatures below about 1080 °C,
copper and nickel are mutually soluble
in each other in the solid state for all
compositions. This complete solubility
is explained by the fact that both Cu
and Ni have the same crystal structure
(FCC), nearly identical atomic radii and
electronegativities, and similar
valences.
➢The copper–nickel system is termed
isomorphous because of this complete
liquid and solid solubility of the two
components.
INTERPRETATION OF PHASE DIAGRAMS
For a binary system of known composition and
temperature that is at equilibrium, at least three
kinds of information are available:
1. the phases that are present,
2. the compositions of these phases, and
3. the percentages or fractions of the phases.
 PHASES PRESENT
• The establishment of what phases
are present is relatively simple. One
just locates the temperature–
composition point on the diagram
and notes the phase(s) with which
the corresponding phase field is
labeled.
• For example, an alloy of
composition 60 wt% Ni–40 wt% Cu
at 1100 °C would be located at
point A; since this is within the
region, only the single phase will
be present. On the other hand, a 35
wt% Ni–65 wt% Cu alloy at 1250 °C
(point B) will consist of both and
liquid phases at equilibrium.
 DETERMINATION OF PHASE COMPOSITIONS
• The first step in the determination of phase
compositions (in terms of the concentrations
of the components) is to locate the
temperature–composition point on the
phase diagram.
• Different methods are used for single- and
two-phase regions. If only one phase is
present, the procedure is trivial: the
composition of this phase is simply the same
as the overall composition of the alloy.
• For example, consider the 60 wt% Ni–40 wt%
Cu alloy at 1100 °C (point A). At this
composition and temperature, only the
phase α is present, having a composition of
60 wt% Ni–40 wt% Cu.
 DETERMINATION OF PHASE COMPOSITIONS
In all two-phase regions one may imagine a
series of horizontal lines, one at every
temperature; each of these is known as a tie line,
or sometimes as an isotherm. These tie lines
extend across the two-phase region and
terminate at the phase boundary lines on either
side.
To compute the equilibrium concentrations of the
two phases, the following procedure is used:
1. A tie line is constructed across the two-phase
region at the temperature of the alloy.
2. The intersections of the tie line and the phase
boundaries on either side are noted.
3. Perpendiculars are dropped from these
intersections to the horizontal composition
axis, from which the composition of each of
the respective phases is read.
 DETERMINATION OF PHASE COMPOSITIONS
• For example, consider again the 35 wt% Ni–65
wt% Cu alloy at 1250 °C, located at point B and
lying within the α + L region.
• Thus, the problem is to determine the
composition (in wt% Ni and Cu) for both the α
and liquid phases. The tie line has been
constructed across the α + L phase region.
• The perpendicular from the intersection of the
tie line with the liquidus boundary meets the
composition axis at 31.5 wt% Ni–68.5 wt% Cu,
which is the composition of the liquid phase,
CL.
• Likewise, for the solidus–tie line intersection,
we find a composition for the solid solution
phase, Cα , of 42.5 wt% Ni–57.5 wt% Cu.
 DETERMINATION OF PHASE AMOUNTS
➢The relative amounts (as fraction or as
percentage) of the phases present at
equilibrium may also be computed with the
aid of phase diagrams.
➢Again, the single- and two-phase situations
must be treated separately.
➢The solution is obvious in the single-phase
region: Since only one phase is present, the
alloy is composed entirely of that phase;
that is, the phase fraction is 1.0 or,
alternatively, the percentage is 100%.
➢From the previous example for the 60 wt%
Ni–40 wt% Cu alloy at 1100 °C (point A),
only the phase is present; hence, the alloy
is completely or 100% .
 DETERMINATION OF PHASE AMOUNTS
If the composition and temperature position is located within a two-
phase region, things are more complex. The tie line must be utilized
in conjunction with a procedure that is often called the lever rule (or
the inverse lever rule), which is applied as follows:
1. The tie line is constructed across the two-phase region at the
temperature of the alloy.
2. The overall alloy composition is located on the tie line.
3. The fraction of one phase is computed by taking the length of tie
line from the overall alloy composition to the phase boundary
for the other phase, and dividing by the total tie line length.
4. The fraction of the other phase is determined in the same
manner.
5. If phase percentages are desired, each phase fraction is
multiplied by 100. When the composition axis is scaled in weight
percent, the phase fractions computed using the lever rule are
mass fractions—the mass (or weight) of a specific phase divided
by the total alloy mass (or weight). The mass of each phase is
computed from the product of each phase fraction and the total
alloy mass.
• Consider again the example shown in
Figure, in which at 1250 °C both α and liquid
phases are present for a 35 wt% Ni–65 wt%
Cu alloy.
• The problem is to compute the fraction of
each of the and liquid phases. The tie line
has been constructed that was used for the
determination of α and L phase
compositions.
• Let the overall alloy composition be located
along the tie line and denoted as C0 , and
mass fractions be represented by WL and
Wα for the respective phases. From the
lever rule, WL may be computed according
to
DETERMINATION OF PHASE AMOUNTS
Composition need be specified
in terms of only one of the
constituents for a binary alloy;
for the computation above,
weight percent nickel will be
used (i.e., C0 35 wt% Ni, C 42.5
wt% Ni, and CL 31.5 wt% Ni),
and
DETERMINATION OF PHASE AMOUNTS
Similarly, for the α phase,
 SOLIDIFICATION AND COOLING
• Because of the chilling action of the mold wall, a
thin skin of solid metal is initially formed at the
interface immediately after pouring.
• Thickness of the skin increases to form a shell
around the molten metal as solidification
progresses inward toward the center of the
cavity. The rate at which freezing proceeds
depends on heat transfer into the mold, as well
as the thermal properties of the metal.
• Since the heat transfer is through the skin and
mold wall, the grains grow inwardly as needles
or spines of solid metal. As these spines enlarge,
lateral branches form, and as these branches
grow, further branches form at right angles to
the first branches.
 SOLIDIFICATION AND COOLING
The solid portions are the dendrite
structures that have formed
sufficiently to trap small islands of
liquid metal in the matrix. The
latter condition is promoted by
factors such as slow heat transfer
out of the hot metal and a wide
difference between liquidus and
solidus temperatures. Gradually,
the liquid islands in the dendrite
matrix solidify as the temperature
of the casting drops to the solidus
for the given alloy composition.
 SOLIDIFICATION AND COOLING
The chemical composition varies throughout
the entire casting. Since the regions of the
casting that freeze first (at the outside near
the mold walls) are richer in one component
than the other, the remaining molten alloy
is deprived of that component by the time
freezing occurs at the interior. Thus, there is
a general segregation through the cross-
section of the casting, sometimes called
ingot segregation, as illustrated in the
figure.
 SHRINKAGE
Shrinkage occurs in three steps:
(1) liquid contraction during
cooling prior to solidification;
(2) contraction during the phase
change from liquid to solid,
called solidification shrinkage;
and
(3) thermal contraction of the
solidified casting during cooling
to room temperature.
 SHRINKAGE
The molten metal immediately
after pouring is shown in part
(0) of the series.
Contraction of the liquid metal
during cooling from pouring
temperature to freezing
temperature causes the height
of the liquid to be reduced from
its starting level as in (1) of the
figure.
 SHRINKAGE
Solidification shrinkage, seen in part
(2), has two effects. First, contraction
causes a further reduction in the
height of the casting. Second, the
amount of liquid metal available to
feed the top center portion of the
casting becomes restricted. This is
usually the last region to freeze, and
the absence of metal creates a void in
the casting at this location.
Once solidified, the casting
experiences further contraction in
height and diameter while cooling, as
in (3).
 SHRINKAGE
• Solidification shrinkage occurs in nearly all metals because the solid
phase has a higher density than the liquid phase. The phase
transformation that accompanies solidification causes a reduction in the
volume per unit weight of metal.
• Pattern-makers account for thermal contraction by making the mold
cavities oversized. The amount by which the mold must be made larger
relative to the final casting size is called the pattern shrinkage
allowance.
 DIRECTIONAL SOLIDIFICATION
Internal chills are small metal parts
placed inside the cavity before pouring
so that the molten metal will solidify
first around these parts. The internal
chill should have a chemical
composition similar to the metal being
poured.
External chills are metal inserts in the
walls of the mold cavity that can remove
heat from the molten metal more
rapidly than the surrounding sand in
order to promote solidification. They are
often used effectively in sections of the
casting that are difficult to feed with
liquid metal, thus encouraging rapid
freezing in these sections while the
connection to liquid metal is still open.
 BINARY EUTECTIC SYSTEMS
• Three single-phase regions are
found on the diagram: α, β,
and liquid.
• The α phase is a solid solution
rich in copper; it has silver as
the solute component and an
FCC crystal structure.
• The β phase solid solution
also has an FCC structure, but
copper is the solute.
 BINARY EUTECTIC SYSTEMS
• The solid solubility limit line
separating the α and α + β phase
regions is termed a solvus line; the
boundary AB between the α and α
+ L fields is the solidus line.
• The maximum solubility of copper
in the β phase, point G (8.8 wt%
Cu), also occurs at 779 °C.
• This horizontal line BEG, which is
parallel to the composition axis
and extends between these
maximum solubility positions, may
also be considered to be a solidus
line; it represents the lowest
temperature at which a liquid
phase may exist for any copper–
silver alloy that is at equilibrium.
 BINARY EUTECTIC SYSTEMS

• Point E is called an invariant

point, which is designated by
the composition CE and
temperature TE; for the copper–
silver system.
• An important reaction occurs
for an alloy of composition CE as
it changes temperature in
passing through TE; this reaction
may be written as follows:
a) Aleación hipoeutéctica de plomo y estaño. b) Aleación hipereutéctica de plomo y
estaño. El componente oscuro es el sólido α, rico en plomo y el constituyente claro es el
sólido β rico en estaño; la estructura laminar fina es el eutéctico (400X).