Chapter 4 Modeling Microstructures in the HAZ of Commercially Pure Titanium

4.1 Background

4.2 Phase Transformations in Titanium

Pure titanium has two phase transitions: an  (hcp)® (bcc) phase transformation

in the solid state at 1155 K and melting at 1941 K. xx In commercially pure grade 2

titanium employed in the present study, the allotropic transformation from a hcp  phase

to a bcc  phase occurs at ~ 1188 K due to the presence of iron, oxygen, and other

impurities.xx

The  phase transformation in titanium can occur by martensitic, 35 massive35-38,

or nucleation and growth35,38 mechanisms. These mechanisms compete with one another

and the mechanism that is ultimately responsible for the phase transformation depends on

the purity of the titanium, its microstructure, and the thermal processing conditions.

A. The  ®  Phase Transformation

The  ®  phase transformation has been studied under continuous cooling

conditions in pure titanium, Ti-O alloys, dilute titanium, and some other titanium based

binary alloys. Cormier et al studied the kinetics of the  ®  phase transformation in

both pure titanium and Ti-O alloys by recording the electrical resistance and the

temperature during quenching the samples. They found that the  ®  transition took

place by a classical nucleation and growth mechanism (e.g. thermally activated process)

at cooling rates less than 3000 K/s. The martensitic transformation mechanism (e.g.

athermal process) can only take place at the cooling rates larger than 3000 K/s.
According to their results, interstitial oxygen at concentrations up to 1.2 at.% has no

significant effect on the type of kinetics of the transformation. Based on their isothermal

dilatometry results, Debuigne et al also suggested that the  ®  phase transformation

take place by classical nucleation and growth mechanism rather than martensitic

transition mechanism.

B. The ® Phase Transformation

Knowledge of the  ® transformation in titanium during heating is much less

than that of the  ®  transformation occurring on cooling. The  ® transformation is

more difficult to characterize because the microstructures that form during heating are

subsequently altered and masked as the material back-transforms during cooling.

Recently, J. W. Elmer et al investigated both the  ® transformation during heating

and the  ®  transformation during cooling in the heat affected zone of commercially

pure titanium weldment by using spatially resolved X-Ray diffraction (SRXRD) method.

This new and unique experimental method can be used for direct observation of phase

transformation and study the kinetics of phase transformations. The details about using

the SRXRD method for investigation of phase transformations in the HAZ of

commercially pure titanium welds are described in the following section.

4.1.2 In-Situ Investigation Phase Distribution in the HAZ

During welding commercially pure titanium, a series of phase transformations

take place in both the FZ and the HAZ. The microstructural history of the FZ is

®®liquid®®, while that of the HAZ is ®®20 In welding processes where

steep thermal gradients exist in the material, it is difficult to directly investigate the solid

state phase transformations that take place. Recently, J. W. Elmer et al. used a novel and

unique method, spatially resolved X-Ray diffraction (SRXRD) method, to directly

observe the phase concentration and constructed a real-time phase distribution in the

HAZ of the commercially pure titanium weldment. The details about the SRXRD

methods are given in literature. The results of the SRXRD data were summarized into the

final HAZ phase map which is shown in Fig. xx.

As the material approaches and then moves away from the heat source, a series of

solid changes will take place in the HAZ and result in several sub microstructural regions

as following: (1) a-Ti that undergoes annealing and recrystallization; (2) completely

recrystallized a-Ti; (3) partially transformed a-Ti, where a-Ti and b-Ti coexist; (4)

single-phase b-Ti; (5) back-transformed a-Ti; and (6) recrystallized a-Ti plus back-

transformed a-Ti. Determination of the phase boundaries existing between these regions

can not only provide phase distribution information, but also important phase transition

kinetics data, which can be used to identify possible phase transformation mechanisms.

For example, the kinetic data of the ® transition during heating and the ®

transition during cooling in titanium are rarely known and their transformation

mechanisms are uncertain. According to the their experimental phase distribution map,

the kinetics for both the ® transition during heating and the ® transition during

cooling in titanium were evaluated. The average time for ® transition at various

locations was estimated to be about 0.91 seconds and the ® transition was conclude to

occur via a massive transformation. On the other hand, the minimum time for the ®

transition during heating was estimated to be about 1.81 seconds. Since oxygen stabilizes
the a phase to higher temperatures, it was suggested that the ® transition during

heating was controlled by the long range diffusion of oxygen. …..

4.2 Calculation of Phase transition in the HAZ

In addition to the real-time experiments, mathematical modeling is necessary to

understand the kinetics of the phase transitions and the phase transition mechanisms

involved during continuous heating and cooling. This is because the spatial distribution

map of phases in the HAZ determined by experimental methods is only valid for

specified welding conditions. When the welding conditions change, a new set of time

consuming experiments need to be undertaken. On the other hand, the mathematical

model can be verified by the available real-time experimental results and then applied for

various welding conditions. A comparison of the experimental results with kinetic data

obtained from modeling assuming each possible mechanism with will enable

identification of the actual phase transformation mechanism.

As a first effort to model the phase transitions in titanium, only the ®

transition during heating was considered in the present paper due to the uniqueness of the

kinetic data that can be obtained from the SRXRD technique. These kinetic data are very

difficult to obtain by traditional methods because the microstructures that form during

heating are subsequently altered by the transformations that take place during cooling.

4.2.1 Possible Phase Transformation Mechanism

The martensitic phase transformation occurs only at high rates, and has been

reported to take place at cooling rates in excess of 3000K/s. 35 This cooling rate far
exceeds those encountered in conventional arc welds and precludes this mechanism.

Massive transformations in titanium have been reported to occur at cooling rates similar

to those of martensitic transformations,35 but also at cooling rates which are well within

the realm of arc welds.38 Conventional nucleation and growth phase transformations with

long range solute partitioning occur only at low cooling rates and are generally believed

to occur with much slower kinetics than massive transformations.36,37

In a previous investigation, SRXRD was used as an in-situ experimental

technique to map the phases that exist around an arc weld in commercially pure

titanium.20 This phase map contains direct evidence of the ® transformation kinetics

in the form of spatial displacements of the product phase with respect to the

thermodynamic transformation isotherm. Results of this study showed that the ®

transformation during heating took place with slower kinetics than the ®

transformation during cooling. From the SRXRD measurements, the ®

transformation was estimated to occur with an interface velocity of 100 m/s,20 which is

consistent with measured interface velocities of massive transformation in dilute titanium

alloys.36 Since massive ® transformations during cooling of titanium and titanium

alloys have been well documented by other investigators, 35-38 this mechanism was

assumed to be responsible for the ® transformation during cooling in titanium arc

welds. The ®transformation, on the other hand, was estimated by the SRXRD

measurements to occur at rates more consistent with long range diffusional growth, 20 but

a thorough investigation of this mechanism was not performed. Since the ®

transformation has not been documented nearly as well as the ® transformation in the

available literature, the transformation kinetics need to be studied in more detail. Here,
we utilize isotherms calculated from the turbulent fluid flow and heat transfer model as

input to a modified JMA kinetic model to study the possible rate controlling steps for the

® phase transformation.

The principal impurities in the grade 2 titanium are O (0.17 wt. %) and Fe (0.14

wt.%). In the previous study, the presence of Fe-rich bcc/omega phase particles

distributed throughout the grains was observed in the starting titanium microstructure. 20

These pre-existing particles appear to provide growth sites for the ® transformation

and also tie up much of the Fe impurities. Therefore, it is likely that the ®

transformation during arc welding takes place by a growth dominated mechanism

whereby nucleation of the  phase is not necessary. Since the ® transformation could

be controlled either by diffusion of titanium or oxygen atoms across the  interface, or

oxygen atoms long range diffusion, each of these possible scenarios will be modeled to

determine which is the most likely to control the ® transformation rate. The three

different scenarios can be summarized as: I - an interface controlled mechanism with

titanium short range diffusion (across the  interface), II - an interface controlled

mechanism with oxygen short range diffusion (across the  interface), and III- a long

range solute partitioning mechanism with oxygen diffusion.

4.2.2 Modified JMA Equation for Non-isothermal Conditions

2.2 Application of JMA equation

The JMA equation is suitable for describing the kinetics of reactions controlled

by the nucleation and growth mechanism.39,40 Therefore, this equation is applicable to

describe the ® transition in titanium for all the mechanisms assumed in the above

three scenarios. The JMA equation under isothermal conditions can be expressed as:24

f  1  exp{[ k (T)( t  t 0 )] n }

(15)

where n is a numerical exponent whose value is determined by the nucleation mode. 41 It

is a constant independent of temperature, provided there is no change in the nucleation

mechanism. On the other hand, k(T) depends on both the nucleation and growth rates and

is therefore highly sensitive to temperature:

 G(T) 
k T  k 0  exp  
 kBT 

(16)

where DG(T) is the total activation energy for nucleation and growth and k 0 is pre-

exponential constant. Since heterogeneous nucleation is assumed in the JMA equation,

the values of k(T), DG(T) and k0 are usually determined by isothermal experiments.

The JMA equation can be modified for the non-isothermal kinetics. 24 The

proposed method used the discretization of the time dependence of the temperature, i.e.

approximation of the continuous temperature-time curves by many isothermal steps, each

of them obeying the isothermal JMA-kinetics. The detailed procedure to derive the

modified JMA equation is available in the literature. 24 The final expression for the

transformed fraction obtained from m subsequent isothermal steps can be expressed as:

  m1  
n

f ( t ( T))  1  exp   k ( T0  lT) t  

  l  0  
(17)
where f(t(T)) stands for the transformed phase fraction under non-isothermal conditions, Dt

is the time step, DT is the temperature change corresponding to each Dt, T0 is the initial

temperature, k is a temperature dependent constant, and m is the total number of the

subsequent isothermal steps.

In order to use equation (17), the temperature dependence of the transformation rate

k(T) and the exponent n have to be specified. The values of k(T) and n are dependent on

the transition mechanism assumed. If the transport of Ti atoms across the interface is

considered to be the limiting step, then the activation energy of the titanium self-diffusion

could be taken as the value of DG(T) in equation (16) to calculate k(T). If the transport of

oxygen atoms across the interface is considered to be the limiting step, then the activation

energy of the oxygen diffusion in titanium could be taken as the value of DG(T). In both

cases, it is assumed that the pre-existing Fe-stabilized bcc/omega phase particles 20 provide

a sufficient density of growth sites so that nucleation of  particles from the a matrix is not

required. Under these zero-nucleation rate conditions, a value of n = 1.5 can be assumed

for the JMA nucleation mode exponent for long range diffusion and n = 3.0 can be

assumed for interface controlled growth.41

The kinetic data used in the JMA model is summarized in Table 2 for three

different scenarios. In all three mechanisms, the pre-exponential constant k 0 in equation

(16) took the same value. This value was estimated from the experimental data in the

literature35 and was found to be 2.18´106. For the purpose of this paper, k 0 will be taken to

be a constant for the ® transformation since the temperature dependence of k 0 is not

known for titanium and also it is believed that the temperature dependence of k 0 can be

considered to be small compared to the exponential term in equation (16).42

4.3.3 Phase Transformation Mechanism for the ® transition

2.2 Calculated phase boundaries

The calculated isotherms of  (1163K) and /liquid (1943K) phase transitions

were imposed on the experimentally determined phase distribution map as shown in Fig.

6(b). It was found that the calculated isotherms matched the phase distribution map very

well. This means that the phase boundaries of  and /liquid can be satisfactorily

predicted by the calculated temperature. The  phase boundary lies at the locations

where -Ti totally transformed to -Ti, as indicated by the arrows in Fig. 6(b). The

prediction of the  phase boundary needs the knowledge of both thermal cycles

and the kinetics of the transformation, and therefore cannot be predicted by the thermal

model alone.

To predict the locations of the  phase boundary, a series of lines parallel

to the welding direction were selected as shown in Fig. 6(b). These lines pass through the

locations where the  phase boundary has been experimentally determined. As the

material approaches the heat source, the ® transition at different locations begins

when the monitoring locations reach the  isotherm (1163K). The extent of ® phase

transformation along these lines were calculated by the combination of the calculated

thermal cycles and the modified JMA equation (17). The calculated thermal cycles

experienced by the material moving along these lines are shown in Fig. 7. From this

figure, the peak temperatures and the time periods above the  isotherm along these

lines can be obtained. The further the line away from the welding center line, the lower

the temperature and the shorter the time period above the  transformation
temperature. The peak temperatures and the time periods above the  isotherm along

these lines are given in detail in Table 4.

After knowing the thermal cycles along the lines parallel to the welding direction,

the extents of phase transformation along these lines can be calculated by equation (17).

Different transition mechanisms assumed were used to predict the  phase

boundary by taking the corresponding values of n and DG(T) in Table 2. For each

mechanism, the times for the completion of the ® transformation along these lines

were calculated. The calculated reaction times for all of the mechanisms are shown in

Table 5. The time for the completion of the ® transformation along a line parallel to

the welding direction can also be obtained experimentally from the phase distribution

map. In this way, the time was calculated by dividing the distance (between the 

isotherm and the experimentally determined location of the  phase boundary

along this line) by the welding speed.

To identify the possible mechanism for the ® transformation, the calculated

times for each assumed mechanism were compared with the times determined from the

experimental phase distribution map, as shown in Fig. 8. It was found that the times

from the phase distribution map agreed well with the calculated times from mechanism I,

in which the ® transition was assumed to be controlled by the transport of Ti atoms

across the interface. The calculated times from mechanisms III, in which the transition

was assumed to be controlled by oxygen long range diffusion, are also approximately

comparable with the experimentally determined times. Significant discrepancies exist

between the experimental determined times and the calculated times from mechanisms II,

in which the transition was assumed to be controlled by the transport of oxygen atoms
across the interface. Through the comparison of the calculated times with the

experimentally determined times, it seems that the ® transition is most likely

controlled by the transport of Ti atoms across the interface.

By adopting the mechanism that the ® transformation was controlled by the

transport of Ti atoms across the interface, the locations of the  phase boundary

along the lines parallel to the welding direction were predicted. The transformed volume

fractions of  phase along the lines were calculated by equation (17) and shown in Fig.

9(a). Depending on the thermal history experienced, the times for the completion of

the® transformation along these lines were different. As expected, the further the line

away from the welding center line, the longer the time for the completion of the

transformation. This can be more clearly observed by comparing the times needed for the

® transformation along different lines as shown in Fig. 9(b). After obtaining the

reaction times along these lines, the distances between the transformation starting points

and the transformation finishing points can be calculated by multiplying the welding

speed with the calculated reactions times. The starting points are the intercepts of the

calculated  isotherm with these lines. Thus, the locations of the  phase

boundary along these lines can be determined and shown as the plain circles in Fig. 6(b).

4.2.5 Summary and Discussions