Precipitate Coarsening

Microstructure of two phase alloy is unstable until the total interfacial energy is minimized High density of small particles - large interfacial energy Lower density of larger particles - smaller interfacial energy System tends to go from large number of smaller precipitates to smaller number of larger precipitates - coarsening Typically, coarsening is the stage following growth Distinguishing feature - during growth the volume fraction of the precipitates is increasing during coarsening volume fraction of precipitates is constant In real systems it might be difcult to exactly pinpoint where growth ends and coarsening begins since in many cases these two processes will take place concurrently Coarsening can lead to depreciation of properties such as strength and could be undesirable Kinetics of coarsening is temperature dependent and is particularly important in the design of materials for high temperature applications There are other factors, both thermodynamic and kinetic, that affect the rate of coarsening, such as the interfacial energy between the precipitate and the matrix, the diffusivity of the solute in the matrix .etc.

1 Phase Transformations

Consider two adjacent spherical precipitates of radii r1 and r2, r1 > r2 From Gibbs-Thompson effect, the G-X curve for precipitate of radius r2 will be pushed up higher in free energy than the precipitate of radius r1 From common tangent construction, composition (X1) of matrix in equilibrium with precipitate of radius r1 and X2 in equilibrium with r2 with X2> X1 Therefore, matrix adjacent to precipitate of radius r2 has higher solute content than matrix adjacent to precipitate of radius r1 Concentration gradient in solute in the matrix - drives diffusion of solute away from precipitate of radius r2 to precipitate of radius r1 Precipitate of radius r2 dissolves and precipitate of radius r1 grows Overall the small particles will dissolve due to diffusion of solute away from these particles while the larger particles will grow due to the diffusion of solute towards these particles - basic mechanism of coarsening 2
Phase Transformations

Mean precipitate radius (r) increases with time during coarsening Assuming that volume diffusion of solute through the matrix is the rate controlling mechanism for coarsening, the following relationship is obeyed:
3 r 3 r0 = kt where

k DXe
r0 is the mean radius at time t = 0, D is the diffusion coefcient of solute in the matrix is the interfacial energy Xe is the equilibrium concentration of solute in matrix (in equilibrium with very large precipitates) D and Xe increases exponentially with increasing temperature Therefore, coarsening rate increases very rapidly with increasing temperature
3 r 3 r0 = kt dr k dt r 2 Smaller the r, faster is the rate of coarsening Smaller precipitates coarsen faster than larger precipitates

In reality sometimes, precipitate coarsening may not follow a linear r3 vs. t relationship, reasons: Diffusion short-circuits such as dislocations, grain boundaries Interface-controlled coarsening - interfacial reaction controlled or trans-interface diffusion controlled in case of diffuse (wide) interfaces Typically coarsening rate depends of k, therefore a combination of D, and, Xe 3
Phase Transformations

Examples of the three cases of low , low Xe, and, low D are discussed below: Low Heat-resistant Nimonic (Ni-Cr) alloys usually contain Al and/or Ti Forms ordered Ni3(Al,Ti) precipitates in the disordered fcc matrix Coherent interfaces between the precipitates and the matrix - low interfacial energy ~ 10 - 30 mJ/m2 Fine precipitates formed and these are stable at high temperatures and do not coarsen much Mist between the precipitates and the matrix is in the range 0 - 0.2% depending on composition Creep rupture life of these alloys can be increased 50 x by decreasing the mist from 0.2% to as close to 0 as possible - alloy composition accordingly controlled - during creep deformation, precipitates with the 0.2% mist lose coherency more easily and then increases and these start coarsening rapidly Low Xe High strength at elevated temperatures also achieved by ne oxide precipitate dispersion in the matrix e.g. W and Ni can be strengthened by adding ne dispersion of thoria (ThO2) Oxides are insoluble in metals, and therefore the Xe in the matrix reduces, coarsening rate is reduced Low D Tempered steels - cementite (Fe3C) distributions coarsen rapidly due to high interstitial diffusivity of C in Fe matrix If a carbide forming alloying element is added as a substitutional alloying element - segregates to the carbide - rate of coarsening is substantially reduced since now limited by the substitutional diffusion of alloying element to carbide Also, if sufcient quantitiy of substitutional carbide formed is added, then more stable carbides formed and this reduced the solubility of C in the matrix - Xe is reduced - coarsening rate is reduced
4 Phase Transformations

Overall Transformation Kinetics - TTT Diagrams Plot of fraction transformed (f) as a function of time and temperature: Temperature-time-transformation (TTT) diagram f varies from 0 to 1 f = f(t,T) depends on: Nucleation rate Growth rate Density and distribution of nucleation sites Overlap of diffusion elds from adjacent transformed regions Impingement of adjacent transformed regions

5 Phase Transformations

For transformations of the type , f is the volume fraction of at any instant during the transformation For transformations of the type '+, f is the volume fraction of at time t divided by the nal volume fraction of After quenching from the high temperature (single phase region) to the transformation temperature, Metastable phase will contain number of nucleation sites (usually heterogeneous) Three possible cases: 1. Constant nucleation rate throughout the transformation - nuclei form throughout the transformation - wide range of particle sizes throughout the transformation - f depends on nucleation rate and growth rate All nuclei form at the beginning of the transformation - site saturation - f depends on number of nucleation sites and growth rate Transformations of type or + (collectively known as cellular transformations) - parent phase completely consumed by the product phase - transformation does not terminate by gradual reduction of growth rate but by impingement of adjacent transformed regions growing with a constant velocity. E.g. Pearlite, cellular precipitation, massive transformation, recrystallization

2.

3.

6 Phase Transformations

Simple derivation of f(t,T): Consider a cellular transformation of the type in which cells are continuously nucleated throughout the transformation at a constant rate N The nuclei grow as spheres at a constant rate v Volume of cells nucleated at the beginning, 4 4 3 V = r 3 = ( vt ) 3 3 Volume of cells nucleated at t = , 4 3 V = v 3 ( t ) 3

7 Phase Transformations

Number of nuclei that formed in the time interval d = N d t 4 3 3 f = V = Nv ( t ) d 3 0

f=

Nv 3t 4 3

Equation holds only for f << 1, early stages of transformation As transformatiom proceeds, regions will start impinging on one another and transformation will slow down. Modied equation for fraction transformed,

f = 1 exp Nv 3t 4 3 f = 1 exp kt

Johnson-Mehl-Avrami equation

The above equation holds because for small values of z << 1,

f = 1 exp( z) z t , f 1
In general,

f = 1 exp kt n

Where n is a numerical exponent with a value varying from ~ 1 to 4 n is independent of temperature provided there is no change in nucleation mechanism k is strongly dependent on the nucleation and growth rate and therefore highly temperature sensitive For the above case,

k=

Nv 3 3

N and v are highly temperature sensitive

8

Phase Transformations

Time for 50% transformtion, f = 0.5 exp(-0.7) = 0.5

n kt 0.5 = 0.7

t 0.5 t 0.5

0.7 1/ n = k 2.1 1/ 4 0.9 = = 1/ 4 3 / 4 Nv 3 N v

Transformation is faster, larger the value of k In the specic case we discussed, this means that transformation is faster for larger values of N and v, as expected Civilian transformations or diffusional transformations typically exhibit a C-shaped TTT transformation curve

Easy to explain based on the variation in nucleation and growth rates as a function of undercooling, At temperatures just below Te (equilibrium transformation temp.), small T, driving force for transformation is small, small nucleation rates, transformation does not proceed fast At lower temperatures, or large T, diffusivity is too low and limits rate of transformation Therefore, maximum rate is obtained at intermediate temperatures
9 Phase Transformations