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    Lecture 18 - Phase Transformations - July 7 2022

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    Ryan Maxwell
    The document discusses phase transformations in materials. It addresses how the rate of transformation depends on time and temperature. It also questions whether non-equilibrium structures can be formed by slowing transformations and if these structures have improved mechanical properties. The document explains that phase transformations are driven by thermodynamics to lower free energy but require time. It describes the nucleation and growth stages of diffusional transformations. Nucleation rates depend on undercooling and can produce different microstructures. Heterogeneous nucleation is favored over homogeneous nucleation due to lower energy barriers. An intermediate undercooling achieves the optimal balance between nucleation and growth rates.

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    Lecture 18 - Phase Transformations - July 7 2022

    Uploaded by

    Ryan Maxwell
    38 views18 pages
    The document discusses phase transformations in materials. It addresses how the rate of transformation depends on time and temperature. It also questions whether non-equilibrium structures can be formed by slowing transformations and if these structures have improved mechanical properties. The document explains that phase transformations are driven by thermodynamics to lower free energy but require time. It describes the nucleation and growth stages of diffusional transformations. Nucleation rates depend on undercooling and can produce different microstructures. Heterogeneous nucleation is favored over homogeneous nucleation due to lower energy barriers. An intermediate undercooling achieves the optimal balance between nucleation and growth rates.

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    Lecture 18_Phase transformations_July 7 2022

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    The document discusses phase transformations in materials. It addresses how the rate of transformation depends on time and temperature. It also questions whether non-equilibrium structures can be formed by slowing transformations and if these structures have improved mechanical properties. The document explains that phase transformations are driven by thermodynamics to lower free energy but require time. It describes the nucleation and growth stages of diffusional transformations. Nucleation rates depend on undercooling and can produce different microstructures. Heterogeneous nucleation is favored over homogeneous nucleation due to lower energy barriers. An intermediate undercooling achieves the optimal balance between nucleation and growth rates.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    38 views18 pages

    Lecture 18 - Phase Transformations - July 7 2022

    Uploaded by

    Ryan Maxwell
    The document discusses phase transformations in materials. It addresses how the rate of transformation depends on time and temperature. It also questions whether non-equilibrium structures can be formed by slowing transformations and if these structures have improved mechanical properties. The document explains that phase transformations are driven by thermodynamics to lower free energy but require time. It describes the nucleation and growth stages of diffusional transformations. Nucleation rates depend on undercooling and can produce different microstructures. Heterogeneous nucleation is favored over homogeneous nucleation due to lower energy barriers. An intermediate undercooling achieves the optimal balance between nucleation and growth rates.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    of 18

    Chapter 10

    Phase transformations
    ISSUES TO ADDRESS...
    •Transforming one phase into another takes time.

    •How does the rate of transformation depend on


    time and temperature?
    •Is it possible to slow down transformations so that non-
    equilibrium structures are formed?
    •Are the mechanical properties of non-equilibrium
    structures more desirable than equilibrium ones?
    Phase diagram of CO2
    Driving forces and time limitations for phase transformations

    • A phase transformation “wants” to occur because of thermodynamics;


    lowering the total free energy (G) is the driving force for a phase
    transformation.

    Phase transformation rate

    • The phase diagram tells you that once the line


    is crossed from liquid to gas then all the water
    should be gas – that is thermodynamics

    • The transition is not instantaneous

    • Processing materials to get desired properties


    Types of phase transformations

    • Involve some alteration of microstructure

    Diffusion Dependent
    Diffusionless
    1. No change in number or
    1. Metastable
    composition of phases present
    phase is
    (solidification of a pure metal,
    produced
    recrystallisation, grain growth)
    2. Change in number/composition
    of phases (Eutectoid reactions)
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    Kinetics of phase transformation

    Phase transformation is a time-dependent process

    Two stages to diffusional phase transformations:

    1. Nucleation stage (the formation of a group of atoms that constitute a small


    nucleus of the phase that can achieve stable growth)

    2. Growth stage (the nucleus grows via mass transport of atoms or molecules to
    and from the growing interface to maintain the composition of the stable phase(s))
    Nucleation

    –nuclei (seeds) act as templates on which crystals grow


    –for the nucleus to form rate of addition of atoms to the nucleus
    must be faster than the rate of loss
    –once nucleated, growth proceeds until equilibrium is attained
    Driving force to nucleate increases as we increase ΔT
    –supercooling(eutectic, eutectoid)

    Small supercooling→slow nucleation rate -few nuclei -


    large crystals
    Large supercooling→rapid nucleation rate -many nuclei -
    small crystals
    Solidification: Nucleation Types

    •Homogeneous nucleation
    –nuclei form in the bulk of liquid metal
    –requires considerable supercooling(typically 80-300°C)

    •Heterogeneous nucleation
    –much easier since a stable “nucleating surface” is
    already present —e.g., mold wall, impurities in liquid
    phase
    –only very slight supercooling(0.1-10°C)
    Nucleation
    To form a stable nucleus that will grow we require a balance of two types of
    energy:

    1) surface energy
    2) volume energy
    • Each increment of volume energy contributes a certain amount of energy (ΔGV)
    to the process.
    • This energy change is negative as it is the driving force for the change (tends to
    lower the overall energy of the system).
    • The energy holding back the transformation is surface energy. It costs energy to
    create new surface, thus surface energy opposes the volume energy term.
    • we have a net result of a barrier - a critical radius exists: if growth is to occur
    the critical radius must be exceeded.
    a) the surface energy term, which varies
    as r2 since the area of a sphere is 4πr2.
    b) the volume energy term, which
    varies as r3 since the volume of a
    sphere is 4/3 π r3.
    c) The sum of the previous two terms
    showing r* and ΔG*.
    d) the change in free energy ΔG with
    small changes in r.. After W.D.Callister.
    For a wetting angle, Ɵ = 0° (complete
    wetting), the function f(Ɵ ) is zero, and there
    is no barrier to nucleation.

    As the value of wetting angle increases to


    180° then the function f(Ɵ ) increases to
    1, at which point there is no difference
    between homogeneous and heterogeneous
    nucleation.

    In between these extremes (0 < Ɵ < 180°)


    heterogeneous nucleation is favoured because
    ΔG* is less:
    Intermediate undercooling has the perfect balance of high nucleation rate
    and decent growth rate and yields a maximum overall phase transformation rate.

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