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Second Chapter




 PHASE DIAGRAM
Phase diagram
• a phase diagram is a type of graph used to show the
  equilibrium conditions between the thermodynamically-
  distinct phases.
• Phase Diagrams, which indicate the phases present at
  a given temperature and composition, have often proved
  a difficult concept to understand.
• These are known as equilibrium diagrams. Temperature
  is plotted on or ordinate (y-axis) and composition (in
  binary phase diagram or pressure (unitary phase
  diagram) on abscissa (x-axis) in the phase diagram.
• The compositions is expressed in % weight. Phase
  diagram are always drawn equilibrium state because the
  system always tries to be stable.
Classification of phase diagrams
• Unary phase diagram (single components
  system).
• Binary phase diagram (two components
  system).
• Tertiary phase diagram (three components
  System).
• Quarter phase diagrams (four components
  systems).
Unary phase diagram (single components system).


The diagram indicated
different phases as a
function of temperature and
pressures. Crystal form of
iron    such     as     BCC
(alpha,α), FCC (Gamma, γ)
and HCC (Delta, δ) are
obtain as increasing the
temperatures. The BCC
form converted to HCP
form near a pressure of
about 125 atm. Above the
eutectic point temperature,
i.e., 9100C BCC converted
to FCC. at a peritectic point
temperature, i.e., 14950C
liquid + HCP converted to       Fig T-P phase diagram for iron. I am not sure that I
FCP.                            believe that there is a critical point for liquid and γ-
Temp range for                  Fe.
BCC = upto 9100C.
FCC = 920-14100C
                   0
Binary phase diagram (two components system).
Such diagram of results of two components
systems.     In    addition    pressure     and
temperature, a third variable, composition is
also involved now. It therefore three
dimensional diagram to depict phases.
However for the simplicity of plotting phase
diagrams on paper; the temperature is
always taken on ordinate and composition
on abscissa for a specified pressure.
The binary diagram of two components are
A and B. Percentage weight components.
Percentage weight composions of A raies
from 0 to 100 from left to right while that of B
varies from between 0 to 100 from right to         A phase diagram for a binary
left on horizental axis named as composition       system displaying a eutectic
or C axis. There are two phase regions, viz        point. The eutectic point is the
the solid and liquid. The solid phase region       point at which the liquid phase
lies middle of the straight line called as tie-    L borders directly on the solid
line. The liquid phase region lies above the       phase α + β.
solid phase lines.
Classification of binary phase
                  diagram
•   Eutectic Phase diagram
•   Eutectoid phase diagram
•   Paritactic phase diagram
•   Peritectoid phase diagram
Eutectic Phase diagram
• An      eutectic     phase
  diagram is obtained when
  the melting point of the
  two components of the
  phase       diagram     are
  neither very close nor
  much different .
• The     eutectic    system
  involves                the
  transformation of a liquid
  phase into two other solid
  phases on cooling and
  vice       versa,      and
  expressed as
•       L (liquid phase) →
  α+β (solid Phase)
Some uses of Eutectic phase diagram
•   Some uses include:
•   eutectic alloys for soldering, composed of tin (Sn), lead (Pb) and sometimes
    silver (Ag) or gold (Au).
•   casting alloys, such as aluminum-silicon and cast iron (at the composition
    for an austenite-cementite eutectic in the iron-carbon system).
•   brazing, where diffusion can remove alloying elements from the joint, so that
    eutectic melting is only possible early in the brazing process.
•   temperature response, i.e. Wood's metal and Field's metal for fire sprinklers.
•   non-toxic mercury replacements, such as galinstan.
•   experimental metallic glasses, with extremely high strength and corrosion
    resistance.
•   eutectic alloys of sodium and potassium (NaK) that are liquid at room
    temperature and used as coolant in experimental
    fast neutron nuclear reactors.
Eutectoid Phase diagram
• In eutectoid system, a
  solid phase replaces the
  liquid phase of eutectic
  system.
• The eutectoid system
  involves               the
  transformation of a solid
  phase into two other solid
  phases on cooling and
  vice       versa,     and
  expressed as
•        γ (solid phase) →
  α+β (solid Phase).
• In the Fe-C system, there
  is a eutectoid point at
  approximately 0.8wt% C,
  723°C.
The compositions of the
two new phases are given
 by the ends of the tie-line
   through the eutectoid
     point. The general
    eutectoid reaction is
          therefore:
Solid γ –> solid α + solid β
 or using the names given
      to these phases:
   Austenite –> ferrite +
     cementite (Fe3C)
Eutectoid
When      the    solution above         the
transformation point is solid, rather than
liquid,    an    analogous       eutectoid
transformation can occur.
For instance, in the iron-carbon system,
the austenite phase can undergo a
eutectoid transformation to produce
ferrite and cementite (iron carbide),
often in lamellar structures such as
pearlite and bainite.
This eutectoid point occurs at 727°C
(1340.6 ºF) and about 0.83% carbon[5];
alloys of nearly this composition are
called high-carbon steel, while those         Iron-carbon phase diagram, showing
which have less carbon are termed             the euctectoid transformation
mild steel. The process analogous to          between austenite (γ) and pearlite.
glass formation in this system is the
martensitic transformation.
Paritactic phase diagram
•   Peritectic transformations are also
    similar to eutectic reactions. Here, a
    liquid and solid phase of fixed
    proportions react at a fixed
    temperature to yield a single solid
    phase.
•   L + β phase → α Phase

•   Since the solid product forms at the
    interface between the two reactants, it
    can form a diffusion barrier and
    generally causes such reactions to
    proceed much more slowly than
    eutectic or eutectoid transformations.
    Because of this, when a peritectic
    composition solidifies it does not show
    the lamellar structure that you find with
    eutectic freezing.
•   Such a transformation exists in the iron
    -carbon system, as seen near the
    upper-left corner of the figure. It
    resembles an inverted eutectic, with
    the δ phase combining with the liquid
    to produce pure austenite at 1495 °C
    and 0.17 mass percent carbon
• Peritectic
• Peritectic transformations are also similar to eutectic
  reactions.
• Here, a liquid and solid phase of fixed proportions react
  at a fixed temperature to yield a single solid phase.
  Since the solid product forms at the interface between
  the two reactants, it can form a diffusion barrier and
  generally causes such reactions to proceed much more
  slowly than eutectic or eutectoid transformations.
  Because of this, when a peritectic composition solidifies
  it does not show the lamellar structure that you find with
  eutectic freezing.
• Such a transformation exists in the iron-carbon system,
  as seen near the upper-left corner of the figure. It
  resembles an inverted eutectic, with the δ phase
  combining with the liquid to produce pure austenite at
  1495 °C and 0.17 mass percent carbon.
Peritectoid phase diagram
• Peritectoid phase diagrams involve
  transformation of two solid phases into a
  different solid phase on cooling and vise
  versa. Contrary peritectic reaction where
  sodid liquid phase L + β changed to another
  solid phase α; here solid phase changed to
  another solid phase. It is given by
• γ + β phase → α solid Phase
Gibbs' phase rule
• Gibbs' phase rule, stated by
  Josiah Willard Gibbs in the 1870s, is the
  fundamental rule on which phase diagrams are
  based.
  F=2−π+C
• where π is the number of phases present in
  equilibrium (Types of solid, liquid, gas phases
  etc). F is the number of degrees of freedom or
  independent variables taken from temperature,
  pressure and composition of the phases
  present. C is the number of chemical
  components required to describe the system
• Condensed phase rule
• In many solids with high melting
  temperature; the vapour pressure of the
  solids and even that of the liquid is
  negligible in comparison with
  atmospheric pressure.
  F=1−π+N
Figure     1    shows     the
equilibrium    diagram     for
combinations of carbon in a
solid solution of iron. The
diagram shows iron and
carbons combined to form
Fe-Fe3C at the 6.67%C end
of the diagram. The left side
of the diagram is pure iron
combined      with    carbon,
resulting in steel alloys.
Three significant regions can
be made relative to the steel
portion of the diagram. They
are the eutectoid E, the
hypoeutectoid A, and the
hypereutectoid B. The right
side of the pure iron line is
carbon in combination with
various forms of iron
called alpha iron (ferrite),
gamma iron (austenite),
and delta iron. The black
dots      mark      clickable
sections of the diagram.         Fig 1: Fe-Fe3C Phase Diagram
                                 Iron-Iron Carbide Phase Diagram
Continue...
•   Allotropic changes take place when there is a change in crystal
    lattice structure. From 2802º-2552ºF the delta iron has a
    body-centered cubic lattice structure.
•   At 2552ºF, the lattice changes from a body-centered cubic to a
    face-centered cubic lattice type.
•   At 1400ºF, the curve shows a plateau but this does not signify
    an allotropic change. It is called the Curie temperature, where
    the metal changes its magnetic properties.
•   Two very important phase changes take place at 0.83%C and at
    4.3% C. At 0.83%C, the transformation is eutectoid, called
    pearlite.
•   gamma (austenite) --> alpha + Fe3C (cementite)
•   At 4.3% C and 2066ºF, the transformation is eutectic, called
    ledeburite.

•   L(liquid) --> gamma (austenite) + Fe3C (cementite)
Home assignments
•   Equilibrium Calculations
    1. Given the Fe-Fe3C phase diagram, Fig. 1, calculate the phases present
       at the eutectoid composition line at:
    a. T = 3000ºF
    b. T = 2200ºF
    c. T = 1333ºF
    d. T = 410ºF
    2. Calculate the phases in the cast-iron portion of the diagram at the
       eutectic composition of 4.3% C in combination with 95.7% ferrite at:
    a. T = 3000ºF
    b. T = 1670ºF
    c. T = 1333ºF
    3. A eutectoid steel (about 0.8%C) is heated to 800ºC (1472ºF) and cooled
       slowly through the eutectoid temperature. Calculate the number of
       grams of carbide that form per 100g of steel.
    4. Determine the amount of pearlite in a 99.5% Fe-0.5%C alloy that is
       cooled slowly from 870ºC given a basis of 100g of alloy.
Lever Rule
•   To determine compositions of
    phases      and     the       relative
    proportions of phases to each
    other in Binary diagrams the
    LEVER RULE is used.
•   Using the lever rule one can
    determine      quantitatively      the
    relative composition of a mixture in
    a     two-phase    region      in    a
    phase diagram. The distances l
    from the mixture point along a
    horizontal tie line to both phase
    boundaries give the composition:
• Nα lα = nβ lβ
•   nα represents the amount of
    phase α and nβ represents the
    amount of phase β.
1. Point "I" lies above the liquidus within the
liquid                                     field.

What is the composition, in terms of the two end
member components, A and B, of the liquid
represented by this point?

To determine the composition of "I" you must
complete       the     following       steps:

1. Draw a line through "I" perpendicular to the
AB join, i.e., the base of the diagram. This line
represents a line of constant composition and is
referred        to      as       an       isopleths.
2. The liquid at "I" consists of a mixture of A and
B, the proportions of which can be determined
simply by measuring the length of three lines,
AI', BI' and AB and then ratio these lengths.
%A = I'B/AB *100
%B = I'A/AB *100
This gives us the bulk composition of the liquid
at this point. If the composition point for the
moves then we get a new bulk composition for
that point represented by the new liquid
Home Assignment

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Phase diagrams

  • 2. Phase diagram • a phase diagram is a type of graph used to show the equilibrium conditions between the thermodynamically- distinct phases. • Phase Diagrams, which indicate the phases present at a given temperature and composition, have often proved a difficult concept to understand. • These are known as equilibrium diagrams. Temperature is plotted on or ordinate (y-axis) and composition (in binary phase diagram or pressure (unitary phase diagram) on abscissa (x-axis) in the phase diagram. • The compositions is expressed in % weight. Phase diagram are always drawn equilibrium state because the system always tries to be stable.
  • 3. Classification of phase diagrams • Unary phase diagram (single components system). • Binary phase diagram (two components system). • Tertiary phase diagram (three components System). • Quarter phase diagrams (four components systems).
  • 4. Unary phase diagram (single components system). The diagram indicated different phases as a function of temperature and pressures. Crystal form of iron such as BCC (alpha,α), FCC (Gamma, γ) and HCC (Delta, δ) are obtain as increasing the temperatures. The BCC form converted to HCP form near a pressure of about 125 atm. Above the eutectic point temperature, i.e., 9100C BCC converted to FCC. at a peritectic point temperature, i.e., 14950C liquid + HCP converted to Fig T-P phase diagram for iron. I am not sure that I FCP. believe that there is a critical point for liquid and γ- Temp range for Fe. BCC = upto 9100C. FCC = 920-14100C 0
  • 5. Binary phase diagram (two components system). Such diagram of results of two components systems. In addition pressure and temperature, a third variable, composition is also involved now. It therefore three dimensional diagram to depict phases. However for the simplicity of plotting phase diagrams on paper; the temperature is always taken on ordinate and composition on abscissa for a specified pressure. The binary diagram of two components are A and B. Percentage weight components. Percentage weight composions of A raies from 0 to 100 from left to right while that of B varies from between 0 to 100 from right to A phase diagram for a binary left on horizental axis named as composition system displaying a eutectic or C axis. There are two phase regions, viz point. The eutectic point is the the solid and liquid. The solid phase region point at which the liquid phase lies middle of the straight line called as tie- L borders directly on the solid line. The liquid phase region lies above the phase α + β. solid phase lines.
  • 6. Classification of binary phase diagram • Eutectic Phase diagram • Eutectoid phase diagram • Paritactic phase diagram • Peritectoid phase diagram
  • 7. Eutectic Phase diagram • An eutectic phase diagram is obtained when the melting point of the two components of the phase diagram are neither very close nor much different . • The eutectic system involves the transformation of a liquid phase into two other solid phases on cooling and vice versa, and expressed as • L (liquid phase) → α+β (solid Phase)
  • 8. Some uses of Eutectic phase diagram • Some uses include: • eutectic alloys for soldering, composed of tin (Sn), lead (Pb) and sometimes silver (Ag) or gold (Au). • casting alloys, such as aluminum-silicon and cast iron (at the composition for an austenite-cementite eutectic in the iron-carbon system). • brazing, where diffusion can remove alloying elements from the joint, so that eutectic melting is only possible early in the brazing process. • temperature response, i.e. Wood's metal and Field's metal for fire sprinklers. • non-toxic mercury replacements, such as galinstan. • experimental metallic glasses, with extremely high strength and corrosion resistance. • eutectic alloys of sodium and potassium (NaK) that are liquid at room temperature and used as coolant in experimental fast neutron nuclear reactors.
  • 9. Eutectoid Phase diagram • In eutectoid system, a solid phase replaces the liquid phase of eutectic system. • The eutectoid system involves the transformation of a solid phase into two other solid phases on cooling and vice versa, and expressed as • γ (solid phase) → α+β (solid Phase). • In the Fe-C system, there is a eutectoid point at approximately 0.8wt% C, 723°C.
  • 10. The compositions of the two new phases are given by the ends of the tie-line through the eutectoid point. The general eutectoid reaction is therefore: Solid γ –> solid α + solid β or using the names given to these phases: Austenite –> ferrite + cementite (Fe3C)
  • 11. Eutectoid When the solution above the transformation point is solid, rather than liquid, an analogous eutectoid transformation can occur. For instance, in the iron-carbon system, the austenite phase can undergo a eutectoid transformation to produce ferrite and cementite (iron carbide), often in lamellar structures such as pearlite and bainite. This eutectoid point occurs at 727°C (1340.6 ºF) and about 0.83% carbon[5]; alloys of nearly this composition are called high-carbon steel, while those Iron-carbon phase diagram, showing which have less carbon are termed the euctectoid transformation mild steel. The process analogous to between austenite (γ) and pearlite. glass formation in this system is the martensitic transformation.
  • 12. Paritactic phase diagram • Peritectic transformations are also similar to eutectic reactions. Here, a liquid and solid phase of fixed proportions react at a fixed temperature to yield a single solid phase. • L + β phase → α Phase • Since the solid product forms at the interface between the two reactants, it can form a diffusion barrier and generally causes such reactions to proceed much more slowly than eutectic or eutectoid transformations. Because of this, when a peritectic composition solidifies it does not show the lamellar structure that you find with eutectic freezing. • Such a transformation exists in the iron -carbon system, as seen near the upper-left corner of the figure. It resembles an inverted eutectic, with the δ phase combining with the liquid to produce pure austenite at 1495 °C and 0.17 mass percent carbon
  • 13. • Peritectic • Peritectic transformations are also similar to eutectic reactions. • Here, a liquid and solid phase of fixed proportions react at a fixed temperature to yield a single solid phase. Since the solid product forms at the interface between the two reactants, it can form a diffusion barrier and generally causes such reactions to proceed much more slowly than eutectic or eutectoid transformations. Because of this, when a peritectic composition solidifies it does not show the lamellar structure that you find with eutectic freezing. • Such a transformation exists in the iron-carbon system, as seen near the upper-left corner of the figure. It resembles an inverted eutectic, with the δ phase combining with the liquid to produce pure austenite at 1495 °C and 0.17 mass percent carbon.
  • 14. Peritectoid phase diagram • Peritectoid phase diagrams involve transformation of two solid phases into a different solid phase on cooling and vise versa. Contrary peritectic reaction where sodid liquid phase L + β changed to another solid phase α; here solid phase changed to another solid phase. It is given by • γ + β phase → α solid Phase
  • 15. Gibbs' phase rule • Gibbs' phase rule, stated by Josiah Willard Gibbs in the 1870s, is the fundamental rule on which phase diagrams are based. F=2−π+C • where π is the number of phases present in equilibrium (Types of solid, liquid, gas phases etc). F is the number of degrees of freedom or independent variables taken from temperature, pressure and composition of the phases present. C is the number of chemical components required to describe the system
  • 16. • Condensed phase rule • In many solids with high melting temperature; the vapour pressure of the solids and even that of the liquid is negligible in comparison with atmospheric pressure. F=1−π+N
  • 17. Figure 1 shows the equilibrium diagram for combinations of carbon in a solid solution of iron. The diagram shows iron and carbons combined to form Fe-Fe3C at the 6.67%C end of the diagram. The left side of the diagram is pure iron combined with carbon, resulting in steel alloys. Three significant regions can be made relative to the steel portion of the diagram. They are the eutectoid E, the hypoeutectoid A, and the hypereutectoid B. The right side of the pure iron line is carbon in combination with various forms of iron called alpha iron (ferrite), gamma iron (austenite), and delta iron. The black dots mark clickable sections of the diagram. Fig 1: Fe-Fe3C Phase Diagram Iron-Iron Carbide Phase Diagram
  • 18. Continue... • Allotropic changes take place when there is a change in crystal lattice structure. From 2802º-2552ºF the delta iron has a body-centered cubic lattice structure. • At 2552ºF, the lattice changes from a body-centered cubic to a face-centered cubic lattice type. • At 1400ºF, the curve shows a plateau but this does not signify an allotropic change. It is called the Curie temperature, where the metal changes its magnetic properties. • Two very important phase changes take place at 0.83%C and at 4.3% C. At 0.83%C, the transformation is eutectoid, called pearlite. • gamma (austenite) --> alpha + Fe3C (cementite) • At 4.3% C and 2066ºF, the transformation is eutectic, called ledeburite. • L(liquid) --> gamma (austenite) + Fe3C (cementite)
  • 19. Home assignments • Equilibrium Calculations 1. Given the Fe-Fe3C phase diagram, Fig. 1, calculate the phases present at the eutectoid composition line at: a. T = 3000ºF b. T = 2200ºF c. T = 1333ºF d. T = 410ºF 2. Calculate the phases in the cast-iron portion of the diagram at the eutectic composition of 4.3% C in combination with 95.7% ferrite at: a. T = 3000ºF b. T = 1670ºF c. T = 1333ºF 3. A eutectoid steel (about 0.8%C) is heated to 800ºC (1472ºF) and cooled slowly through the eutectoid temperature. Calculate the number of grams of carbide that form per 100g of steel. 4. Determine the amount of pearlite in a 99.5% Fe-0.5%C alloy that is cooled slowly from 870ºC given a basis of 100g of alloy.
  • 20. Lever Rule • To determine compositions of phases and the relative proportions of phases to each other in Binary diagrams the LEVER RULE is used. • Using the lever rule one can determine quantitatively the relative composition of a mixture in a two-phase region in a phase diagram. The distances l from the mixture point along a horizontal tie line to both phase boundaries give the composition: • Nα lα = nβ lβ • nα represents the amount of phase α and nβ represents the amount of phase β.
  • 21. 1. Point "I" lies above the liquidus within the liquid field. What is the composition, in terms of the two end member components, A and B, of the liquid represented by this point? To determine the composition of "I" you must complete the following steps: 1. Draw a line through "I" perpendicular to the AB join, i.e., the base of the diagram. This line represents a line of constant composition and is referred to as an isopleths. 2. The liquid at "I" consists of a mixture of A and B, the proportions of which can be determined simply by measuring the length of three lines, AI', BI' and AB and then ratio these lengths. %A = I'B/AB *100 %B = I'A/AB *100 This gives us the bulk composition of the liquid at this point. If the composition point for the moves then we get a new bulk composition for that point represented by the new liquid