Research Summary

Titanium

Modeling Thermodynamics, Kinetics,

and Phase Transformation Morphology
While Heat Treating Titanium Alloys
Savko Malinov and Wei Sha

This article summarizes research work

on computer modeling of thermodynamics and kinetics of phase transformation
behavior in a number of titanium alloys,
carried out in collaboration with TIMET
UK. The goal is to model the microstructural evolution of the alpha/beta phases
as a function of heat treatment and alloy
chemistry including ve major titanium
alloys. The results of the research include
time-temperature-transformation and
continuous cooling diagrams. Experimental validation, by measurement of
the kinetics of growth and dissolution
of alpha and other phases, has been
conducted.
INTRODUCTION
The increasing application of titanium
alloys is due to their very good combination of mechanical properties and
corrosion as well as erosion resistance.
Although the aerospace industry still provides the major market, titanium and its
alloys are currently nding widespread
applications in many areas, such as
chemical and engineering industries, as
structural materials for more general pur-

poses. The advantages of titanium alloys

include: low density, giving very attractive strength-to-weight ratio allowing
lighter and stronger structures; superior
corrosion and erosion resistance in many
environments; and high-temperature
capability. Although titanium materials
are considered to be expensive materials,
for many applications the cost of titanium
alloys can be justied because of their
desirable properties. Titanium alloys
are desirable and sometimes essential
for structural applications at elevated
temperature.
It is widely understood that the
mechanical properties of titanium
alloys are very sensitive to the characteristics of the microstructure. The type
of phases, grain size and grain shape,
morphology, and distribution of the
ne microstructure ( + colonies)
determine the properties and therefore
the application of titanium alloys. The
nal microstructure is formed during the
thermo-mechanical and heat treatment
processing. It is therefore important to
understand the correlation processing
parameters microstructure proper-

ties, which would allow the optimization

of the processing parameters and alloy
composition in order to achieve the
desired combination of properties for any
particular application. At present, this is
one of the most challenging areas in the
research on titanium alloys. It must be
pointed out however, that the relationship
between the processing parameters and
the mechanical properties for titanium
alloys has so far mainly been studied
empirically, which is both costly and
time consuming. The idea of computer
modeling and simulation of the different
processes taking place during processing
of titanium alloys is very attractive and
highly desirable.
The main aim of this work is to create
computer-based models for modeling
different correlations and phenomena
of processing-microstructure-property
for titanium alloys. The eventual target
was to create a tool for optimization of
the processing parameters and the alloy
composition. See the sidebar for experimental and modeling methodology.
MAIN RESULTS AND
DISCUSSION
Thermodynamics

50 m

20 m

Figure 1. The microstructures of Ti 6-2-4-2 alloy after different temperatures of isothermal

exposure.

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In titanium alloys, there are different

equilibrium amounts of and phases
as well as equilibrium compositions of
both phases at different temperatures.
The experimental study of the thermodynamic equilibria was mainly performed
by microscopy examinations of samples
after different heat treatments.14,68 Phase
equilibria were also calculated for the
titanium alloys in wide temperature
ranges2,7,8 with Thermo-Calc software
and using the titanium database. The
calculated results were compared with
experimental results obtained from different experimental techniques. A good
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EXPERIMENTAL AND MODELING METHODOLOGY

The modeling work is largely based on experimental results. Five commercial titanium
alloys were used as experimental materials, namely Ti-6Al-4V (TIMETAL 6-4) ,15 Ti6Al-2Sn-4Zr-2Mo (TIMETAL 6-2-4-2),2,3,5,6 Ti-8Al-1Mo-1V (TIMETAL 8-1-1),7 Ti10V-2Fe-3Al (TIMETAL 10-2-3), and Beta21s (TIMETAL 21s).3,8,9 Most materials were
provided by the main industrial collaborator involved in this project, TIMET UK Ltd. The
alloy behavior was studied in different heat-treatment and microstructural conditions.
Details of the alloy compositions, their heat treatment, and microstructural conditions
are given in the corresponding references. These alloys were selected, rst, because they
are the most commonly used commercial titanium alloys and second, because they are
representatives of the different classes of titanium alloys: , near-, + , and .
Experimental techniques used were differential scanning calorimetry; resistivity;
microscopy, both optical (including high-temperature in-situ microscopy) and scanning
electron microscopy; and x-ray diffraction, using both conventional and synchrotron
radiation.
A variety of computation and modeling techniques and approaches were adopted to
model the different phenomena and correlations during processing of titanium alloys.
Thermodynamic calculations were performed to calculate the phase equilibria.2,6,7,8,10
Kinetics of phase transformation in different alloys and processing conditions were
modeled by developing software and modules, in the frame of Johnson-Mehl-Avrami
theory.1,2,68 Finite element modeling is used to model the morphology of the microstructure
and the beta to alpha phase transformation during different processing cycles.11

agreement between the experimental

and calculated phase compositions was
found for the Ti 6-4 alloy. For the other
alloys, there were larger differences
between experimental and calculated
values. Possible explanations of these
differences were suggested. The thermodynamic calculations suggested that
the transformation is controlled by diffusional redistribution of different alloying elements between and phases
depending on the alloy. The results of the
thermodynamics were explained based
on the pseudo binary phase diagram of
titanium alloys. The phase equilibria
results were used as input modules of
the general models for the phase
transformation (see next section).
The transus temperature in titanium
alloys was modeled using thermodynamic calculations.10 The results agree
with experimental results.

8-1-1,7 Ti 10-2-3, and Beta21s8 alloys at

isothermal conditions were studied using
in-situ electrical resistivity. The
samples were cooled rapidly from the
temperature of the homogenization to
the chosen holding temperature and then
isothermally held at this temperature.

Then, the resistometric signal was

recorded. Curves tracing the course of
the phase transformation at different
temperatures were recorded.
Different mechanisms of the -phase
formation depending on the temperature
of isothermal exposure were proposed
for Ti 6-4 and Ti 6-2-4-2 alloys. For
isothermal exposure at temperatures
above 900C, mainly grain boundary
formed by nucleation and growth (Figure
1a). For a high degree of undercooling
(temperatures below 900C), mixed
mechanisms of the transformation were
observed. The main part was homogeneously nucleated (within the former
-grains) and plate-like grown (Figure
1b).
The kinetics were modeled within the
framework of the Avrami theory by
means of the Johnson-Mehl-Avrami
(JMA) equation. The theory was adapted
depending on the different mechanisms
of phase nucleation and growth. The
JMA kinetic parameters for different
temperatures, alloys, and conditions of
the described transformation were
obtained by logarithmic plots of
ln(ln(1/(1y))) versus ln(t), y and t being

Figure 2. The experimental and

calculated kinetics of the + phase
transformation at different temperatures
for Ti-8Al-1Mo-1V alloy.

Kinetics
Previously, there was no comprehensive knowledge of the phase transformation kinetics in the variety of the titanium
alloys in different time-temperature
regimes. One of the purposes of this
project was to model the kinetics of
the + phase transformation in
different titanium alloys under different
processing conditions.
Time-Temperature Transformation

Figure 3. The calculated thermokinetics diagram of the temperature

of transformation vs. cooling rate for
Ti 6-4. Isolines show the isotransformed fractions.

The kinetics of the + phase

transformation in Ti 6-4, Ti 6-2-4-2,2 Ti
2005 September JOM

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Continuous-Cooling Transformation

The JMA kinetic parameters were

derived from DSC experiments with
constant cooling rates. However, once
obtained, these parameters can be used
to trace the course of transformation in real practice for a non-uniform
cooling rate. Based on the derived kinetic
parameters, a model was created for
monitoring the transformation
during continuous cooling with an arbitrary cooling path (Figure 5).6 The input
for the model is the cooling path, which
can be user dened or input from a real
furnace. The kinetic parameters as well
as the data on the thermodynamic equilibria are incorporated in the model.
Utilizing the cooling laws, kinetic parameters, and thermodynamic equilibria, the
transformation process is calculated and
displayed. The calculations are performed using the JMA model under the
principles of additivity taking into
account the phase equilibrium condiOUTPUT

Continuous Cooling Path

(Temperature Time Curve)

Kinetics
Parameters

Thermodynamic
Equilibria

Monitoring the Kinetics of

Transformation
(Transformed Fraction
as a Function of the
Time/Temperature)

The Model
Time

From Furnace or
Arbitrary User Defined
Cooling Path

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A Model for Simulation and

Monitoring of the
Transformation on Continuous
Cooling

INPUT

The kinetics of transformation

in Ti 6-41 and Ti 6-2-4-26 alloys were
studied using differential scanning calorimetry (DSC) under continuous-cooling
conditions. The results were used to
calculate the degree of transformation
as a function of the time or the temperature. The calculated curves of
transformed fraction versus temperature

and errors were minimized using the

sum-square-error technique.
As the next step in this work, the
transformed fractions for different cooling rates were calculated using the
derived kinetic parameters. Very good
correspondence between calculated and
experimental transformed fraction was
found (Figure 4). These parameters can
be used to trace the course of
transformation in real practice for whatever (not necessarily constant) cooling
path.

Fraction

the degree of transformation and time,

respectively as well as with a program
to minimize the sum square error between
experimental and calculated fractions.
In Figure 2, the experimental transformation kinetics are compared for different
constant temperatures. Agreement was
found for all alloys studied. This provided
condence in the obtained JMA kinetic
parameters.
Complete time-temperature-transformation (TTT) diagrams were designed
for the + transformation in the
alloys studied. Such diagrams are useful
in alloy heat treatment practice. In the
literature, usually only the start and the
end of the transformation are plotted in
these diagrams. It should be noted that
for the titanium alloys studied the end
of transformation does not correspond
to the complete transformation of the
initial phase to the new phase. At
each temperature a different phase composition ( + mixture) is the nal
product. Iso-lines were calculated and
plotted on the same diagrams, showing
the real amounts of the phase. The
TTT diagrams designed were compared
with existing experimental data (where
available), with good agreement.

Temperature

Figure 4.The experimental and calculated

degree of transformation in Ti 6-4
for different cooling.

and of transformed fraction versus time

trace the course of the transformation at continuous-cooling conditions.
Thermo-kinetic diagrams were calculated showing lines of iso-transformed
fraction as temperature vs. cooling rate
(Figure 3). Such thermo-kinetic diagrams
are useful tools to trace the course of
transformation in a real product where
the cooling rates in a (usually quite large)
piece vary signicantly from the surface
to the core. Based on the DSC results,
continuous-cooling transformation
(CCT) diagrams were calculated. In these
diagrams, iso-lines of equal transformed
fractions for the different cooling rates
are given. The CCT diagrams are calculated for cases of cooling from different
temperatures.
The results from calorimetry were
used to trace and model the transformation kinetics in continuous-cooling
conditions. The kinetics of transformation were modeled adopting the JMA
theory for non-isothermal transformation. The T-t path of continuous cooling
is replaced by the sum of small, consecutive isothermal steps. For each
isothermal stage, JMA theory for isothermal phase transformations is applied.
These calculations present a numerical
solution of the general expression of the
concept of additivity formulated by J.W.
Cahn.
Based on the provided description, a
computer program was written and used
to derive the optimized JMA kinetic
parameters at different temperatures
from the DSC results. The transformed
fractions measured experimentally were
compared with the calculated fractions,

Time/Temperature

Figure 5. A block diagram of a model for tracing the

transformation on continuous cooling for Ti6Al-2Sn-4Zr-2Mo-0.08Si alloy.

JOM September 2005

Figure 6. Finite-element method simulations for the microstructure evolution of the phase
transformation in Ti-6Al-4V alloy at continuous cooling with constant cooling rate of 5C/min.
assuming colony growth in three different directions. The scale to the right represents
vanadium concentration.

tions. In this way, the transformation

process can be followed for any cooling
path. An option is incorporated into the
model to enable it to be linked to a real
furnace. In this case, the cooling path of
the furnace is read into the model as an
ASCII data le. Thus, the transformation
process is monitored in real-time. The
model created could provide useful
insights into such processes.
Morphology
In thermodynamics and kinetics modeling, the phase transformation process
is considered mainly in terms of the
quantity of phases present but not their
geometry and morphology. However,
different morphologies of the phases
present determine a completely different
combination of mechanical properties
even if the amounts of the phases are the
same. Considering this throughout the
project, the authors focused on experimental study and computer modeling of
the morphology of phase transformations
in titanium alloys at different processing
conditions.
The experimental work was mainly
performed by means of in-situ hightemperature study, on an optical microscope equipped with a high-temperature
stage and using both normal and orescence light.5 The changes taking place
on the sample surface during the experiments were monitored. The morphology
of the phase transformation
was recorded at different heat-treatment
conditions using the effect of thermal
etching. An effect of sample surface
oxidation and deoxidation was observed
during continuous heating. The appear2005 September JOM

ance and disappearance of ordered

titanium oxides Ti3O and Ti2O were
discussed within the framework of the
phase equilibrium diagram. The kinetics
of the surface oxidation were monitored
in both isothermal and continuous-cooling conditions.
In this project, a mathematical model
and computer programs were developed
for numerical simulation of the processes
of nucleation and growth of the phase
Widmansttten plates during the course
of the phase transformation in
Ti-6Al-4V11 and Ti-6Al-2Sn-4Zr-2Mo
alloys. The phase appearance at the
grain boundary of phase is described
by a numerical procedure for random
nucleation as a function of the alloying
elements concentration and the temperature. The rate at which an interface
moves depends both on the intrinsic
mobility and on the rate at which diffusion can remove the excess of stabilizing alloying elements atoms ahead of
the interface. Finite-element modeling
and the volume-of-uids method were
used to obtain numerical solutions to the
problem for localization and evolution
of the / interface. The elements chosen
have dimensions in both space and time.
Computer program packages were developed for solving the one-dimensional
and two-dimensional problems for
nucleation and growth of the -phase
Widmansttten plates in the phase.
The packages developed were used to
simulate the microstructural morphology
during different heat-treatment conditions. The effects of the cooling rate and
the temperature on the microstructure
were predicted and analyzed. A good

correspondence between the model

simulations and experimental data is
observed regarding the lamellae thickness; the kinetics of the phase
transformation; the rate of nucleation of
the phase; and the simulated phase
equilibria. The results simulating the
grain boundary phase colonies growing in different directions are presented
in Figure 6.
References
1. S. Malinov et al., Metallurgical and Materials
Transactions A, 32A (2001), pp. 879887.
2. S. Malinov et al., Journal of Alloys and Compounds,
314 (2001), pp. 181192.
3. S. Malinov et al., Materials Characterization, 48
(2002), pp. 279295.
4. W. Sha and Z. Guo, Journal of Alloys and
Compounds, 290 (1999), pp. L3L7.
5. S. Malinov, W. Sha, and C.S. Voon, Journal of
Microscopy, 207 (2002), pp. 163168.
6. S. Malinov et al., Titanium Alloys at Elevated
Temperature: Structural Development and Service
Behaviour, ed. M. Winston (London: Institute of
Materials, 2001), pp. 6988.
7. S. Malinov, P. Markovsky, and W. Sha, Journal of
Alloys and Compounds, 333 (2002), pp. 122132.
8. S. Malinov, W. Sha, and P. Markovsky, Journal of
Alloys and Compounds, 348 (2003), pp. 110118.
9. W. Sha and C.J. McKinven, Journal of Alloys and
Compounds, 335 (2002), pp. L16L20.
10. Z. Guo and W. Sha, Titanium 99: Science and
Technology, Vol. 1, ed. I.V. Gorynin and S.S. Ushkov
(St. Petersburg, Russia: Central Research Institute of
Structural Materials, 2000), pp. 6168.
11. I. Katzarov, S. Malinov, and W. Sha, Metallurgical
and Materials Transactions A, 33A (2002), pp. 1027
1040.
Savko Malinov is with the School of Aeronautical
and Mechanical Engineering at the Queens
University of Belfast.
For more information, contact Wei Sha, Metals
Research Group, School of Civil Engineering,
Architecture and Planning, the Queens University
of Belfast, Belfast BT7 1NN, U.K.; e-mail
w.sha@qub.ac.uk.

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