MTE 449 Powder Metallurgy

Chapter 4 Solidification and Microstructure of Atomized Powders

Nagy El-Kaddah

Analysis of Solidification Processes

To produce the desired microstructure of the powder in atomization processes, one need to control process variables that influence the rate of solidification of the atomized droplets The first step toward this goal is to identify key solidification parameters through the analysis of heat transfer processes and nucleation and growth kinetics in the droplet Due to complexity of solidification phenomena, the analysis should involve every available experimentally developed relationships for describing microstructure features of the material system

Formulation of Heat Transfer Problem for a Droplet

For an atomized metal droplet in tens of microns size range, due to high thermal conductivity, the rate of heat flow from the droplet to the surround is controlled principally by convective resistance with practically no temperature gradient in the droplet. By assuming that the droplet is space wise isothermal and temperature varying only with time, from overall energy balance, the temperature history of the droplet is given by c p ,l T Tl
dT = A ( qconv + qrad ) V C dt
* p

L C = c p + Tl Ts c p ,s
* p

Tl > T > Ts T Ts

qconv = hconv ( T To ) qrad = ( T 4 To4 ) = hrad ( T To ); hrad = ( T 2 To2 ) ( T + To )

where V and A are volume and surface area of the droplet, Cp is specific heat, L is latent heat of fusion, To is room temperature, hconv and hrad are convective and radiation heat transfer coefficients, is Stefan-Boltzmann constant and is emissivity of material

Calculation of Cooling Rate and Solidification Time

Cooling Rate

Calculation of the cooling rate to predict the grain structure of solidified the particle is based on the cooling rate of the droplet at the liquidus temperature (TM), which may be written as
dT 6k = ( hconv + hrad ) ( TM To ) c p ,l DV dt

where DV is equivalent volume diameter and k is shape factor. The convective heat transfer coefficient, hconv, may be estimated from the following correlation
Nu = 0.0266 Re0.805 Pr1 / 3 V D h D Nu = conv V Re = g g V g Kg Pr = c p,g g Kg

where KV is thermal conductivity of the surrounding gas

The temperature history of droplet during cooling from its initial temperature to its freezing temperature is given by
6 k (hconv + hrad ) t T To = exp Ti To c p ,l DV

Calculation of Cooling Rate and Solidification Time (cont.)

Solidification time

Solidification time is the time taken to cool the droplet to the liquidus temperature and to freeze the droplet. The cooling time can be evaluated from temperature history equation when the droplet reached TM c p ,l DV Ti To
tC = 6 k ( hconv + hrad ) ln T T o M

Since the latent heat is much higher than the specific heat, the freezing time can be directly estimated by equating total heat losses to total heat released during solidification L DV
tf = 6 k (hconv + hrad ) (TM To )

From these two equation the solidification time is

tS = Ti To L ln + c p ,l (T T ) 6 k ( hconv + hrad ) T T o M o M

DV

Prediction of Grain Structure

For all solidification processes except rotating disk, the structure of solidified powders is dendritic, and dependence of the secondary arm spacing, which relates to the grain size, on the cooling rate (class 8) is given by
dT = C dt
n

where C and n are constants specific to the alloy. The value of n is between 0.5 and 1

From the above analysis, the process variables affecting cooling rate, and hence the grain structure are

Size of the droplet Droplet velocity Temperature of the melt Gas used in the atomization chamber

Typical Cooling Rates and Microstructure Characteristics of Atomized Steel Powders

Process Gas atomization Centrifugal atomization Water atomization Melt explosion

D50, m 75 150 1000 650

, m 2 3 7 7

dT/dt, C/s 2. 104 5. 103 4. 102 4. 102

h, J/m2.s.C 1. 103 5. 103 3. 103 2. 103

Nucleation and Growth Kinetics

Solidification starts with nucleation of the solid in the melt and followed by growth of formed nuclei. Nucleation It is a non-equilibrium process, and transformation of the liquid to solid takes place in under cooled liquid below its melting points. The deviation of the bulk free energy of the liquid from its equilibrium value at the melting point (Gv = Go T) causes the atoms to form solid clusters in the melt (homogeneous nucleation) or to deposit on the surface of dispersed solid phases such as nonmetallic inclusions in the melt (heterogeneous nucleation) Homogeneous Nucleation Theory Clustering of the atoms is a probabilistic process involving clustering few atoms to form a solid phase and the growth of the cluster (diffusion). This process involves an increase of the energy of the cluster due to the formation a new surface (surface energy) As a result not all formed clusters survive, only the ones (nuclei) which do not increase the energy of the system

Nucleation and Growth Kinetics (cont.)

Homogeneous Nucleation Theory (cont.) The condition for formation of a stable cluster

The critical size nucleus

1. 2.

The rate nucleation is determined from

4 R 3 Gv + 4 R 2 3 3 R = Gv

=0

Extent of deviation from equilibrium state, i.e. (Gv) Rate of growth of initially formed cluster to its critical size

Undercooling has opposite effects on these two kinetic parameters. Higher undercooling favors formation of clusters through Gv, and hinders growth by slowing mobility of atoms
3 2 E 16 TM exp I = I o exp kT 3 k H 2 T T 2 f

where Io is nucleation rate constant and E is activation energy for atom motion

nucleation rate, I

Maximum nucleation rate occur at moderate undercooling High undercooling suppress nucleation and favors solidification of amorphous metals

Nucleation and Growth Kinetics

Heterogeneous Nucleation The heterogeneous solid phases in melt act as nuclei if they overcome interfacial barrier to form a grow on them Based on this concept a number of models were proposed to predict nucleation rate in terms to

Number of available heterogeneous particles in the melt (Ns) Undercooling of the melt and empirical growth rate constants ().
2 I = N s 1 exp T 2

Hunts model

Growth Kinetics The growth of formed nuclei is described empirically in terms of undercooling
dR = T 2 dt

The nucleation and growth theories are foundation of all solidification models for predicting grain and microstructure of solidified materials.

Time-Temperature-Transformation (TTT) diagram

The TTT diagram provides a practical way to predict solidified phases and their amounts for any material during cooling It maps the times for nuclei to form and to grow in crystalline phase as function of temperature. The shortest nucleation time is intermediate undercooling where nucleation rate is maximum. The form phases are determined from superimposing the cooling rate from heat transfer analysis
path i normal cooling, crystalline solid path ii rapid solidification, amorphous solid path iii partial transformation, mixed microstructure; some crystals and some amorphous path iv atomization with intermediate quench - gives all amorphous

Effect of Particle Size on Amorphous/Crystalline Ratio

Smaller particles have higher cooling rates than larger ones They are more likely to experience high undercooling which favors solidification of amorphous structure The percentage of amorphous phase increases with

Decreasing particle size Increasing heat transfer coefficient by using gases with higher thermal conductivity such as H2 and He.