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    Study Material - MMC402 PDF

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    JISSNU KUNDU
    The document discusses constructing phase diagrams from free energy vs composition diagrams. It explains that the curvature of the solid and liquid lines are different, resulting in two cutting points rather than one as in an isomorphous system. This leads to either a minimum arising if the solid curvature is less than the liquid, or vice versa. The procedure is similar to constructing isomorphous and eutectic systems. The document also discusses superlattices, miscibility gaps, nucleation and growth, and how varying the nucleation and growth rates affects the resulting grain structure.

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    Study Material - MMC402 PDF

    Uploaded by

    JISSNU KUNDU
    56 views11 pages
    The document discusses constructing phase diagrams from free energy vs composition diagrams. It explains that the curvature of the solid and liquid lines are different, resulting in two cutting points rather than one as in an isomorphous system. This leads to either a minimum arising if the solid curvature is less than the liquid, or vice versa. The procedure is similar to constructing isomorphous and eutectic systems. The document also discusses superlattices, miscibility gaps, nucleation and growth, and how varying the nucleation and growth rates affects the resulting grain structure.

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    The document discusses constructing phase diagrams from free energy vs composition diagrams. It explains that the curvature of the solid and liquid lines are different, resulting in two cutting points rather than one as in an isomorphous system. This leads to either a minimum arising if the solid curvature is less than the liquid, or vice versa. The procedure is similar to constructing isomorphous and eutectic systems. The document also discusses superlattices, miscibility gaps, nucleation and growth, and how varying the nucleation and growth rates affects the resulting grain structure.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    56 views11 pages

    Study Material - MMC402 PDF

    Uploaded by

    JISSNU KUNDU
    The document discusses constructing phase diagrams from free energy vs composition diagrams. It explains that the curvature of the solid and liquid lines are different, resulting in two cutting points rather than one as in an isomorphous system. This leads to either a minimum arising if the solid curvature is less than the liquid, or vice versa. The procedure is similar to constructing isomorphous and eutectic systems. The document also discusses superlattices, miscibility gaps, nucleation and growth, and how varying the nucleation and growth rates affects the resulting grain structure.

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    You are on page 1of 11

    Construction of phase diagram from free energy vs composition diagram

    (continued):

    Earlier we had constructed isomorphous phase diagram. Here carefully look at the curvature
    of free energy vs composition diagram. Curvature of solid and liquid is different. So we get
    two cutting points (recall isomorphous system, we get one cutting point) here. If the curvature
    of solid < curvature of liquid a minimum arises (top part of the figure) and the reverse
    (bottom part of the figure).
    Remember the procedure of constructing the phase diagram here from free energy vs
    composition diagram is similar as we had discussed earlier for the isomorphous system (will
    be same for eutectic system as well).
    Note that it is not similar like binary eutectic (given below) as here we do not have two
    different solid solutions (like eutectic). Here only one type of solid solution (one crystal
    structure) exists.

    1
    Constructing eutectic phase diagram:

    Both diagrams are similar. Just for more clarity.


    The procedure is similar like before. Note that here we have two different types of solid
    solutions (two terminal solid solutions).

    2
    Superlattices and miscibility gap:

    3
    Look at figure 11.9 (Au-Ni phase diagram). At high temperature we have liquid phase. At
    lower temperature we have single phase solid solution (disordered). Upon decreasing
    temperature we can find three different phases (Au 3Cu, AuCu and AuCu 3). These are called
    superlattice (ordered) phase.
    Look at figure 11.10. Recall our earlier discussion on mole fraction/activity composition. Due
    to –ve deviation here unlike atom pair (Au-Cu) is preferred than like atoms (Cu-Cu or Au-
    Au). However, at higher temperature we have only short range order as thermal vibration
    does not allow long range ordering. As temperature decreases further we have long range
    order of unlike atom pairs. Then it is called superlattice.
    Now look at figure 11.11. Here we have two grains (dark like of grain boundary). Now look
    at each grain. We have three domains in the upper grain where we have only unlike pairs of
    atoms. And two domains are separated by a boundary where we have similar atom pairs. This
    boundary is called antiphase boundary.

    Now come to Au-Ni phase diagram. Below liquid phase we have single phase solid solution.
    However, at lower temperature you can see a two phase region (1 and 2). Both have fcc
    structure but differ in lattice parameter, density etc. One phase is based on Au lattice and
    another is on Ni. This type of region is termed as miscibility gap.

    4
    Nucleation and growth:

    Let’s consider simple solidification of a pure metal from its liquid state.

    Now consider the change in free energy during solidification (Liquid to solid change, i.e.
    cooling).

    Gv – volume free energy change


    L and S denote liquid and solid
    L – latent heat
    ΔT – undercooling required to start solidification.

    5
    Note: Carefully check the free energy change as a function of temperature and see the
    stability of solid and liquid.

    Now nucleation is of two types homogeneous (no external surface is present) and
    heterogeneous (nucleation occurs over a external surface, here over the mould wall).

    Homogeneous nucleation

    Here, look at the free energy before solidification starts (G1) and after a cluster forms (G2).
    Energy is calculated based on the creation of new solid particle (new surface and a change in
    volume for both solid and liquid). Carefully check the change in volume in the system due to
    creation of the new solid cluster.
    Now change in free energy (ΔG=G2 – G1) is expressed in terms of solid radius.
    Next we plot ΔG as a function of r.

    6
    From the equation we can find r* (critical radius where d/dr (ΔG) = 0). At r=r*, ΔG= ΔG*.
    Now look at the ΔG vs r plot and we can deduce

    7
    Effect of undercooling on r

    8
    Heterogeneous Nucleation

    Here, nucleation occurs over an external surface (Nucleating agent).

    Note that due to the presence of external surface (mould) we have few interfacial energy
    terms which was not there in homogeneous nucleation like solid-mould, liquid-mould. The
    interfacial energy term is different here in comparison to homogeneous nucleation
    accordingly.
    Next we derive the change in free energy in the similar manner as that of homogeneous
    nucleation.

    9
    See the relation between ΔG heterogeneous and ΔG homogeneous. ΔG heterogeneous < ΔGhomogeneous as the
    factor S(θ) is less than unity.
    Now let us derive r* and ΔG*.

    Note that there is no change in r* in comparison to homogeneous nucleation. So r* does not


    depend on type of nucleation (heterogeneous or homogeneous). It only depends on
    undercooling. However, ΔG* decreases.

    10
    Nucleation and growth rate and corresponding structure:

    Coarse grain

    Fine grain
    grain

    Low nucleation rate and high growth rate – Coarse grain structure
    High nucleation rate and low growth rate – Fine grain structure – Important for synthesizing
    nano-materials, metallic glass etc.

    11

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