Materials Science and Engineering A243 (1998) 206 211

Phase transformations during cooling in a +b titanium alloys

T. Ahmed, H. J. Rack *
Department of Ceramic and Materials Engineering, School of Chemical and Materials Engineering, Clemson Uni6ersity, 204 Olin Hall, Clemson,
SC 29634 -0907, USA

Abstract
A simplified methodology for investigating the effects of cooling rate from elevated temperature on phase transformations
observed in a+ b titanium alloys is described. It involves adaptation and refinement of a circumferentially insulated and
instrumented Jominy end quench bar, timetemperature profiles obtained during cooling at locations along the bar length
providing a complete thermal history. The ability of this procedure to examine the phase transformation for a + b titanium alloys
has been demonstrated in Ti6Al4V where varying cooling rates from 525 to 1.5C s 1 are shown to result in a series of
martensitic, massive and diffusional phase transformations. Cooling rates above 410C s 1 result in a fully martensitic
microstructure, a massive transformation being observed between 410 and 20C s 1, this transformation being gradually replaced
by diffusion controlled Widmanstatten a formation with decreasing cooling rate. 1998 Elsevier Science S.A. All rights reserved.

1. Introduction

2. Experimental methods

Although a +b titanium alloys are presently most

often used in the mill annealed condition, many previous investigators have shown that substantial benefits
in yield, tensile and fatigue strengths can be achieved
when these materials are solution treated and aged.
Further, substantial component cost reductions have
been projected if complex structures can be assembled
using advanced fabrication techniques, e.g. superplastic
forming plus diffusion bonding, particularly if these
structures do not require subsequent re-heat treatment.
Finally increasing interest has recently been shown in
replacement of heavy section steel airframe members by
titanium alloys.
In all these instances a fundamental understanding of
the phase transformations occurring during thermal
processing, particularly during cooling from elevated
temperature, is required if optimal mechanical performance of a+ b titanium alloys is to be achieved. Results of an on-going investigation into the phase
transformations occurring during cooling of a + b titanium alloys are reported herein-the methodology employed and results for Ti 6Al 4V quenched from
above the b transus being presented.

Prior studies of phase transformations during cooling

have historically used multiple samples, cooling rates
being descriptively defined as air, water, fan air, furnace
cooled, etc. The present investigation has quantified
this approach through adaptation of an experimental
technique, the end quench Jominy procedure [1], long
used by ferrous alloy producers. Ti6Al4V(Ti
6.04Al4.03V0.12Fe0.09O0.03C0.009N23 ppm
H) received as a 31.8 mm diameter bar was used to
develop and refine the methodology. Following sample
fabrication, thermocouples were welded along the
length of the Jominy bar, the sample coated with BN to
minimize oxidation during solution treatment and
finally insulted with a Kaowool insulating barrier, the
latter to insure one-dimensional heat flow during subsequent cooling. Continuous monitoring of the thermocouples permitted determination of the sample
temperaturetime history during cooling, cooling rates
as a function of location and temperature being derived
therefrom. The samples were equilibrated at a predetermined solution treatment temperaturethe results of b
solution treatment being presented in this publicationand transferred to a stand where either water or
forced gas cooling was provided. A typical temperaturetime excursion during helium gas quenching is
shown in Fig. 1.

* Corresponding author. Tel.: +1 864 6565636; fax: + 1 864

6564466.
0921-5093/98/$19.00 1998 Elsevier Science S.A. All rights reserved.
PII S 0 9 2 1 - 5 0 9 3 ( 9 7 ) 0 0 8 0 2 - 2

T. Ahmed, H.J. Rack / Materials Science and Engineering A243 (1998) 206211

207

Fig. 1. Representative cooling curves for Ti6Al4V solution treated for 30 min at 1050C and helium gas quenched. Thermocouple distance from
quenched end (a) 3.2, (b) 9.5, (c) 12 and (d) 15.2 mm.

Fig. 2. Optical and TEM micrographs of a% martensite formation in Ti 6Al 4V cooled at 525C s 1 illustrating (a) orthogonal a% plate, (b)
dislocations, (c) stacking fault and (d) twin substructure.

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T. Ahmed, H.J. Rack / Materials Science and Engineering A243 (1998) 206211

Fig. 3. Massive a formation in Ti 6Al 4V cooled at (a) 410, (b) 275, (c) 175 and (d) 20C s 1.

Following cooling, optical, scanning, transmission

and X-ray diffraction observations were performed
with samples cut from the quenched Jominy bar at
known locations, and thus known cooling rates. Optical
microstructures were prepared by either mechanically
polishing or electro-polishing. Electro-polishing typically used a solution of 10 ml H2SO4 and 90 ml
methanol under voltage and temperature conditions of
1525 V and 010C, the polished samples then being
etched, for optical examination, with 1.5 vol.% HF, 3.5
vol.% HNO3 and distilled H2O.
Thin foil samples for transmission electron microscopy (TEM) were prepared from the surfaces adjacent to optical samples by mechanical waffering,
grinding to 0.15 mm thickness and electro-polishing in
a solution similar to that used for bulk polishing under
the voltage and temperature conditions of 15 20 V and
40C. Finally X-ray diffraction analysis utilized
CuKa radiation operated at 40 kV and 30 mA, the
scanning rate being 5 2u min 1, from 2u = 2080.

3. Results and discussion

Hexagonal,a%, martensite formation was observed at
highest cooling rate (defined at 900C) attained, 525C
s 1. Its morphological features are illustrated in Fig. 2,
the a% being composed of long orthogonally oriented
martensitic plates having an acicular morphology, and
a substructure containing predominately dislocations
and stacking faults with a few platelets containing
twins. These results agree with those reported by Blackburn and Williams [2], and more recently by Gil et al.
[3], the predominance of dislocations and stacking
faults indicating that the relaxation of the invariant
strain accompanying the a% transformation is primarily
accomplished by formation and migration of perfect
and partial dislocations.
At slightly lower cooling rates (410C s 1) preferential grain boundary formation of a second a morphology was observed in Ti6Al4V, Fig. 3. Continued
reductions in cooling rate resulted in an increase in the

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209

Fig. 4. TEM micrographs illustrating massive a formation in Ti 6Al 4V cooled at (a) 275, (b)175 and (c), (d) 20C s 1 {ZA =[0001]am}.

volume fraction of this a morphology, nucleation of this

phase progressively occurring with decreasing cooling
rate at prior b boundaries, at martensite plates adjacent
to the prior b grain boundaries and ultimately, at the
slowest cooling rates where this transformation was
observed, at individual a% plates within the grains. TEM
confirmed this nucleation sequence and showed that this
a morphology had a blocky appearance with a heavily
dislocated internal substructure; Fig. 4. Selected area
diffraction analysis further confirmed that this blocky a
had a hexagonal crystal structure, identical to that of the
acicular a% martensite observed at higher cooling rates.
Table 1
Qualitative EDX analysis of Ti6Al4V
Cooling rate(C s1)

275
175
20

Phase

a%
am
a%
am
a%
am

Chemical composition
(wt.%)
Al

8.0
8.3
7.1
7.0
7.3
7.6

3.2
3.0
3.1
3.2
2.7
2.7

The crystallographic and morphological features associated with this secondary a morphology suggest that
it has formed as a type 4 competitive massive transformation as originally proposed for the TiV system by
Plichta et al. [4]. In this scheme the massive transformation occurs at a sufficiently low transformation temperatures where the trans-interphase boundary diffusion
rates associated with the massive transformation are
high in comparison with the volumetic diffusion rates
that control growth of equilibrium a. Additionally,
these investigators [5] have shown that, under these
circumstances, the temperature for initiation of the
massive transformation in TiAg, TiAu and TiSi
increases as the cooling rate decreases, suggesting that
the volume fraction of massive a should increase with
decreasing cooling rate, in agreement with the present
observations. Confirmation of this massive transformation path is also provided by qualitative EDX analysis
of sections cooled at rates of 275, 175 and 20C s 1,
Table 1. While absolute solute contents were not, because of uncorrected elemental interaction, provided by
this technique these qualitative results do show that,
within experimental limits, both a morphologies have
similar compositions, thereby fulfilling the final criteria
for a massive transformation [46].

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T. Ahmed, H.J. Rack / Materials Science and Engineering A243 (1998) 206211

Fig. 5. Widmanstatten a formation in Ti 6Al 4V cooled at (a), (b) 15 and (c) 1.5C s 1.

The competitive character of the b am transformation relative to diffusional a formation was confirmed
at slower cooling rates, i.e. B20C s 1, where the
former transformation was absent, heterogeneous nucleation of a grain boundary a layer being observed,
Fig. 5. This a layer was of two types, type 1 having a
zig-zagged appearance, left grain boundary in Fig. 5,
type 2 having a smoother more normal appearance,
right grain boundary. The intra-granular microstructure at this cooling rate was composed of long parallel
primary a plates with secondary plates and retained b
between the a plates. Finally, decreasing cooling rate to
the lowest examined in this study, 1.5C s 1, resulted in
further growth of the grain boundary Widmanstatten a
plates into the center of grains and formation of the
classical basketweave Widmanstatten morphology.
Further examination indicated that the morphology
of the Widmanstatten a associated with the type 1 grain
boundary a layer appeared to have nucleated near or at
the prior b grain boundary. In contrast, the Widmanstatten a associated with type 2 boundary layers

seemed to have grown from the normal grain

boundary a layer. The presence of these apparently
differing a allotriomorphs support the early observations of Aaronson et al. [7] who showed that two types
of Widmanstatten a exist in TiCr, and by inference,
other titanium alloys. These authors, as well as the
more recent results of others [8,9,11] indicated that the
higher temperature allotriomorphs are sympathetically
nucleated with growth controlled by volumetric diffusion [12]as depicted in this investigation by the formation of Widmanstatten a from type 2 boundaries. At
lower reaction temperatures volumetric diffusion is limited, therefore growth appears to be controlled by
interfacial diffusion and ledgewise diffusional growth
[8,10]. The morphological features of the Widmanstatten a transformation associated with the type 1 zig-zag
boundary layer are also consistent with those reported
by Ohmori et al. [13] who showed that this morphology
develops in Ti6Al4V upon isothermal reaction at
temperatures below 925C. These authors indicated
that the zig-zag appearance is characteristic of the low

T. Ahmed, H.J. Rack / Materials Science and Engineering A243 (1998) 206211

211

martensitic, massive and diffusion controlled phase

transformations are observed, cooling rates above
410C s 1 being required to achieved a fully martensitic microstructure, a massive transformation being
observed between 410 and 20C s 1, this transformation being gradually replaced by diffusion controlled
Widmanstatten a formation.

Acknowledgements
The authors would like to acknowledge the funding
support of this research by NASA-Langley Research
Center under contract NAS1-2020.

Fig. 6. Schematic continuous cooling diagram for Ti6Al4V b-solution treated at 1050C for 30 min (Ms temperature due to Majdic and
Ziegler [14]).

temperature regime and proposed that it results from

separate heterogeneous nucleation and growth events
occurring on the pre-exiting prior b grain boundary,
each growing a plate maintaining a Burgers relationship with its parent b matrix. Finally growth and
coalescence of one a variant results in complete
boundary coverage.
The present results can be summarized in the form a
schematic continuous cooling diagram, Fig. 6. This
diagram shows that cooling rates in excess of 410C
s 1 are required for Ti 6Al 4V to attain a completely
martensitic microstructure, lower cooling rates resulting
in mixed microstructures of martensitic a%, massive a
and various morphological forms of diffusion controlled a.

4. Conclusions
This investigation has shown that adaptation and
refinement of a simplified Jominy end quench specimen
allows easy investigation of cooling rate on phase transformation in a+ b titanium alloys. This procedure has
been successfully demonstrated for Ti 6Al 4V where

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