Before going onto the non-equilibrium Fe-C system we will examine the kinetics of phase transformations.! ! !
Solid State Reactions !
Solid State Transformation: When a solid phase(s) changes into another solid phase(s). ! Transformations occur in two steps:! ! Nucleation: ! Growth:
Kinetics: Study of the rate of a transformation or reaction.! ! The effects of kinetics on the phase transformations in Fe-C system leads to:! ! ! ! ! !
the appearance of small particles of the new phase! the growth of the new phase particles!
NEW phases.! NEW microstructures! NEW phases and microstructures mean NEW properties! I KNEW it!!
Transformations are both time and temperature dependent.!
! Temperature! ! Time!
What controls the rate at which phase transformations occur?!
MSE 273 Unit 13 ! 32 ! MSE 273 Unit 13 ! 33 !
Solid State Reactions !
We are rst after the nucleation rate, N.! ! !
Solid State Reactions !
Homogeneous Nucleation: Is the result of an energy balance between the surface energy of the new phase particle !, which increases energy of the system, and the lowering of energy due to the volume of the new phase "Gv, which lowers energy of the system.!
Nucleation:! ! Homogeneous:
Inside parent phase.! ! Heterogeneous: On inhomogeneities like container surfaces, other phase, etc.! ! Example:
As an example lets look at simple phase transformation, solidication below the melting point of a material by homogeneous nucleation. But this could just as easily be a solid state transformation from one solid phase to another.!
4 !G = "r 3!G v + 4"r 2 # 3
MSE 273 Unit 13 !
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MSE 273 Unit 13 !
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Solid State Reactions !
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Solid State Reactions !
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Its clear that the surface energy term will increase with the radius of the particle as r2 and the volume energy term will decrease as r3. The total free energy of the system, "G, is sum of these curves.!
Examination of the summation curve shows that there is a critical radius, r*, above which the free energy of the system decreases with growth of the new phase particle. ! ! Once ! Below
a particle gets to this size, it will grow spontaneously! this size it is unstable and will shrink!
Associated with this critical radius is a critical free energy, "G*. This is the activation energy, or the energy required to form a stable new phase nuclei (particle) that will grow.!
MSE 273 Unit 13 !
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MSE 273 Unit 13 !
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Solid State Reactions !
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Solid State Reactions !
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The temperature at which this solidication occurs (below the melting temperature) will affect the r*.!
Heterogeneous Nucleation: Skipping the mathematics and going right to the results.!
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The critical radius and free energy decrease as temperature decreases. !
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Physically that means that the lower the temperature below the transformation temperature the higher the nucleation rate!! MSE 273 Unit 13 ! 38 !
Physically this curve indicates that heterogeneous nucleation occurs more readily that homogeneous nucleation.! MSE 273 Unit 13 ! 39 !
Solid State Reactions !
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Solid State Reactions !
So the time and temperature dependence of nucleation is given by the nucleation rate N below:!
Nucleation Rate: The nucleation rate for homogeneous nucleation is dependent on both the free energy change (we just did it) and the diffusion of atoms to the particle. Both are temperature dependent. ! $ #G * ' $ Q ' ! N ! exp & " ) exp & " diffusion ) % k BT ( % k BT ( ! !
The diffusional part is given by the second term: ! Unlike the free energy term, however, diffusion term decreases with decreasing temperature.! Graphing this function:!
! MSE 273 Unit 13 ! 40 ! MSE 273 Unit 13 ! 41 !
Solid State Reactions !
We are after the growth rate, G.! ! ! Growth: Occurs once the small new phase particle reaches its critical radius and becomes a stable nucleus. ! ! Growth Rate: Since it often requires long range atomic motion, growth rate is controlled by diffusion. ! ! !
Solid State Reactions !
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Transformation Rate: The rate and which a transformation proceeds is summarized below as a function of temperature.!
# Q & ! G ! exp % " diffusion ( $ k BT '
Obviously growth rate decreases with decreasing temperature.!
Graphing the growth rate And nucleation rate functions yields the transformation rate! MSE 273 Unit 13 ! 42 ! MSE 273 Unit 13 ! 43 !
Solid State Reactions !
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Solid State Reactions !
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Conclusion: Most transformations do not take place instantaneously, they take time and depend on temperature.! ! To
change phases and microstructures, critical size particles must form and atoms must diffuse to them.!
Time-Transformation Curves: At constant temperature the rate at which a phase transforms occurs can be plotted as a function of time. The result is a sigmoidal curve and the Avrami equation.! y = 1! exp !kt n
Where the fraction transformed, y, is dependent on time independent constant, k and n for any particular reaction or transformation.! MSE 273 Unit 13 ! 45 !
MSE 273 Unit 13 !
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Solid State Reactions !
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Solid State Reactions !
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Sigmoidal transformation curve:!
Temperature: Once you cross a phase boundary, the higher the temperature within the new phase eld, the faster the transformation will occur if it is limited by diffusion (shown) it will proceed more slowly, however, if it is controlled by nucleation (not shown).! ! MSE 273 Unit 13 ! 47 !
