Corrosion Science, Vol. 36, No. 4, pp.

631-642, 1994
~ ) Pergamon Copyright© 1994 Elsevier ScienceLtd
Printed in Great Britain. All rights reserved
0010-938X/94 $6.00 + 0.(10

0010-938X(93)E0006-D

AIR OXIDATION BEHAVIOUR OF Ti-6A1-4V ALLOY

BETWEEN 650 AND 850°C

H . L. D u , P. K . DATTA, D . B . LEWIS* a n d J. S. BURNELL-GRAY

Surface Engineering Research Group, University of Northumbria at Newcastle, U.K.

*Materials Research Institute, Sheffield Hallam Univcrsity, U.K.

Abstract--The air oxidation behaviour of Ti-6A1-4V alloy was studied in the temperature range
650-850°C. Continuous oxidation kinetics showed that the alloy oxidised according to a parabolic rate law
at 650 and 700°C after a transient period, whilst at 750 and 800°C, linear-parabolic kinetics dominated, At
850°C, after 50 h linear-parabolic oxidation, the alloy followed a parabolic rate law. The multilayered
oxide scales formed on the oxidised alloy consisted of alternate layers of Al203 and TiO 2 . The number of
Al203 and TiO 2 layers increased with increasing exposure time and temperature. The external gas/oxide
interface was always occupied by an AI203 layer whilst TiO2 always appeared at the oxide/substrate
interface.

INTRODUCTION
Ti-6A1--4V ALLOY is recognised as a work horse material in the aero engine
industries. 1 It is also one of the potential matrix materials in metal matrix composites
reinforced by SiC fibres which are expected to be utilised at temperatures up to
900°C. A survey of relevant open literature revealed an incomplete database on the
oxidation behaviour of this alloy in both air and pure oxygen atmospheres, although
some investigations have been carried out on the oxidation behaviour of Ti-A1
binary alloys 2-s and effects of ternary elements added singly or in combination. 9-13
The results derived from the oxidation of Ti-A1 binary alloys are controversial.
Menzies and Stratford 2 studied the oxidation behaviour of Ti-SAI in CO2 at 1000°C
and indicated that this alloy oxidised more rapidly than pure titanium. However,
Jenkins 3 showed that Ti-3AI alloy exposed to pure oxygen at temperatures between
750 and 900°C oxidised more slowly than did pure titanium, which was attributed to
the formation of a protective scale of alumina due to the preferential oxidation of
aluminium. Other workers 4-7 also found that the addition of aluminium to titanium
enhanced the oxidation resistance since aluminium reduced the amount of oxygen
dissolved in ct-Ti; in detail it was reported 7 that the solubility of oxygen in titanium
was reduced from 34 at% to 0.3 at% at 700°C. An a-AI203 layer was found near the
external interface and alumina was distributed in distinct sublayers of variable
thickness. The number of alumina sublayers decreased with increasing temperature
and above 950°C only an external alumina was identified. Other studies 8 revealed
that alumina existed near the external interface either in the alpha or gamma form.
Some efforts have been made to promote the formation of an external alumina
layer by the addition of ternary elements. It is believed that the ability of Ti-AI alloys
to develop a protective A1203 layer should be increased by (1) increasing the

Manuscript received 27 August 1993.

631
632 H.L. Duet al.

diffusion of AI; (2) reducing the solubility and diffusion of oxygen and (3) decreasing
or eliminating the transient periods. Accordingly, the positive effects of Nb, 9'1° Ta,
Ag, 11 W 9'12 and Re, Mo, Cr 12 on the oxidation behaviour of Ti-A1 binary alloys have
been reported. Hf had only a marginal effect whilst Ga proved to be detrimental. 9
The addition of 1.4 wt% V was observed to prevent the formation of the A120 3
barrier at the interface of inner/outer layers and the oxidation rate increased. 1°
Wallance et al. 13 studied the oxidation behaviour of T i - 2 5 A l - 1 0 N b - 3 V - 1 M o (at%)
alloy in air over a temperature range of 650-1000°C and showed that additions of V
and Mo did not substantially change the oxidation behaviour of this alloy compared
to that observed for Ti-24AI-10Nb, but its overall oxidation rate was much lower
than that for Ti3A1.
The main objective of this work was to study the oxidation behaviour of the T i -
6 A I - 4 V alloy in air within the temperature interval 650-850°C.

EXPERIMENTAL METHOD
The Ti~SA1--4Valloy, employed in this study, was supplied by IMI Titanium Ltd as IMI Titanium
318. *The specimens were machinedfrom a rod into couponsof 12.5 mm diameter with 1.5 mm thickness.
A 1 mm diameter hole was drilled near the edge of each sample to facilitate suspensionwithin the furnace.
All coupons were polished using SiC paper up to 1200 grit followed by 30 rain ultrasonic cleaning and
degreasing in acetone.
The oxidation experiments were carried out in circulating air between 650 and 850°Cfor exposure
periods of up to 100 h. Continuous oxidation kinetics were recorded using a Linseis high temperature
balance. The oxidised specimens were characterised using scanning electron microscopy(SEM), energy
dispersive analysis by X-ray (EDAX) and X-ray diffraction (XRD).

EXPERIMENTAL RESULTS
Oxidation kinetics
The weight gains observed for the Ti-6A1-4V alloy plotted against exposure time
between 650 and 850°C are displayed in Fig. 1. The oxidation kinetics for the T i - 6 A i -
4V alloy can be represented by the relationship:

yn = Knt (1)
where y = weight gain per unit area
n = reaction index
Kn = reaction constant
t = exposure time.
Thus the reaction index, n, can be obtained from the reciprocals of the gradients of
the log/log plots of weight gain (y) versus exposure time (t), as shown in Fig. 2.
Figures 1 and 2 indicate that, at 650 and 700°C, after a logarithmic period (about
120 rain) of oxidation, the oxidation of the Ti-6A1--4V alloy followed a parabolic rate
law ( n - 2 ) . With increasing reaction temperatures, oxidation tended towards
linear-parabolic rate kinetics. For example, at 750°C a 1.61 reaction index was
calculated after about 120 rain of parabolic-cubic period (n = 2.62). At 800°C, after
a short period ( - 3 0 min) of parabolic--cubic oxidation, the oxidation kinetics
exhibited a reaction index of 1.66 between 30 and 1200 min. After longer exposure,
the reaction index decreased to 1.36, which indicated an increased oxidation rate. At
850°C, three stages of reaction kinetics were observed. The alloy oxidised at a

*The specific composition was not available.

 Air oxidation behaviour of Ti-6AI~-IV 633

40 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

35~ ~ 850Oc

; 8oo°c

5,

o ~ ~ - - ~ - - 7-- . - . 6,o~o
0 600 1200 1800 2400 3000 3600 4200 4800 5400 6000 6600
Time (minutes)

FIG. l. Weight gain against time for Ti-6A1-4V alloy oxidised in air between 650 and
850°C.

relatively slow rate (n = 1.66) at the first stage, then a faster oxidation rate was
recorded (n = 1.43). Finally parabolic kinetics were indicated after 3000 rain ex-
posure.
According to the Arrhenius law
Kn = K~,oexp(-EJRT) (2)

I O0 :, . <.. . . . . . ..................... ~ 100

. . . . . .

I I ~ 65oOc

7OOOC ? , . ~
- 7500C
. 8000C
~-" 1Or.
E r
/ 850 OC ~ ,~,'b~
-¢" ~'" ~t10
E

V
• ~,.~
x:
._~
,~2~. ~- ~.~

0.1 -
..... . . . . ......... 20,
t 10 100 1000 10000
Time (minutes)
FiG. 2. Log weight gain versus log time for the air oxidised Ti-6AI~4V alloy between 650
and 850°C; the slope of the curve gives the reaction index.
634 H.L. Du etal.

1000
!

"~ 100~
E
0 L

F
lO
- fL
=O p
X
.¢

O
-.I ,2

0.1 ~ L ~_ t ±

8.5 9 9.5 10 10.5 11

1/Txl0-4(K)
FIG. 3. Arrhenius plot for the air oxidised Ti-6AI-4V alloy.

where Kn,0 is a constant and R is the gas constant. The activation energy (Ea) for the
oxidation of Ti-6AI-4V alloy was obtained by plotting reaction constants, log K n,
against the reciprocals of the reaction temperatures, as shown in Fig. 3. Here it
should be pointed out that because no exact parabolic reaction index (n = 2) was
recorded in the temparture range 650-850°C, the Kp values were obtained by
averaging all the reaction rate constants for various exposure periods. This gave a
value of 267 kJ mo1-1 (64 kcal mo1-1) for the activation energy of the oxidation of
Ti--6AI-4V alloy. This value of E a correlates well with the results of Chaze and
Coddet 7 who investigated air oxidation behaviour of the Ti-(1.65, 3.5 and 5)AI
binary alloys and obtained an activation energy of 277 kJ mo1-1 for the three alloys.

Characterisation of the oxide scales

Figure 4 shows representative surface morphologies of the Ti-6A1-4V alloy after
air oxidation. It is apparent that nodular AI203 nuclei developed on the sample
surface at an early stage of oxidation together with a thin film of TiO2 (Fig. 4a). The
A1203 nuclei grew laterally with increasing exposure time and completely covered
the TiO 2. The alumina was persistently visible at the end of the experiment (100 h).
Also similar morphological features were observed on the oxidised specimens
exposed at different reaction temperatures, e.g. compare Fig. 4(b) and (c) where the
convoluted features of the oxide scale are evidenced. XRD analysis of oxidised
samples for different exposure periods and temperatures identified the presence of
only a-Ai203 and TiO 2 (ruffle), and there was no evidence of the formation of
nitrides as described by Becker et ai.1°
Figures 5-7 represent the EDAX results for the oxidised Ti-6AI--4V alloy. All
results showed an a-Al203 layer on the external interface of the oxide scales for all
oxidised samples. It is interesting to note that a titania layer was always present at the
interface of oxide scale and substrate, whilst an alumina layer formed at the external
gas/oxide interface. The A1203 layer and TiO2 layer grew alternately and thus
producing a multilayered oxide scale on the Ti-6A1--4V alloy. The number of
FIG. 4. Scanning electron micrographs showing typical surface morphologies of Ti-6AI-
4V alloy after air oxidation. (a) 650°C and 5 h, (b) 750°C and 100 h and (c) 850°C and 100 h.

635
 lOpm
i, i

FIG. 5. Electron image and Digimaps showing typical compositional profiles through the
scale on Ti-6AI-4V alloy after air oxidation at 650°C for 100 h.

636
 201Jm
l I
4

FI(;. 6. Electron image and Digimaps showing typical compositional profiles through the
scale on Ti-6AI-4V alloy after air oxidation at 750°C for 100 h.

637
 ~Ja~di~ lO0~m
I i

F1C. 7. Electron image and Digimaps showing typical compositional profiles through the
scale on Ti-6AI-4V alloy after air oxidation at 850°C for 100 h.

638
 Air oxidation behaviour of Ti-6AI-4V 639

alumina and titania layers in the oxide scale increased with increasing oxidation time
and reaction temperature. For example, after 100 h exposure one and four alumina
layers were observed at 650°C (Fig. 5) and 750°C (Fig. 6), respectively. However,
after 100 h oxidation at 850°C, more A1203 layers were found (Fig. 7). Metallo-
graphic examination of the scales also showed that cracking occurred between the
A120 3 and TiO2 layers, as revealed in Figs 6 and 7.

DISCUSSION
The results for the oxidation of Ti-6A1-4V alloy in air between 650 and 850°C
demonstrated that A1203 and TiO2 layers grew alternately and comprised the
multilayered structure of the oxide scale. This indicates that two reactions took place
during the oxidation process of the Ti-6A1-4V alloy:
2Al(l) + 3/202(g) = A1203(s) (3)
Ti(s) + O2(g) = TiO2(s). (4)
For both reactions, the values of standard free energies (J mo1-1) with temperature
(T in Kelvin) can be obtained from the following equations: 14
AG°3,T = --1,676,000 + 320T (5)
AG°4,T = --910,000 + 173T. (6)
Also,

AG~, T = - R T I n Ks = - / , ' T l n -aAI2°-~ (7)

, ---- (aA|)2. ( / ) 0 2 ) 3/2

AG°4,T = - R T l n K 4 .= - R T I n aTiO'- (8)

aTi "pO2'
where K 3 and K 4 are the equilibrium constants for reactions (3) and (4). In the
present situation, it is reasonable to ascribe unit activities to A120 3 and TiO2 and
approximately atmospheric pressure for p O > then equations (7) and (8) become:
AG~.T = - R T I n (aAl) -2 = 2RTln aAi (9)
AG°4.r = - R T I n (awl) i = R T I n avi. (10)
Thus, the minimum values of aluminium activity (ami n A I ) for the formation of Al203
and titanium activity (ami n Ti) for the formation of TiO2, given in Table 1, can be
calculated from equations (9) and (10).
It can be noted that the values of minimum aluminium activity, arnin AI, are
approximately three orders of magnitude greater than the values of minimum

TABLE 1. T H E CALCULATED MINIMUM VALUES OF aAl AND a r i FOR THE FORMATION OF

A I 2 0 3 AND T i O 2 A T p O 2 = 0 . 2 1 a t m BETWEEN 6 5 0 AND 8 5 0 ° C

650°C 700°C 750°C 800°C 850°C

aAI 2.8 X 10 -39 7.6 X 10 -37 1.2 x 10-35 1.2 X 10 -32 7.7 X 10 -31
aTi 1.6 X 10 -42 7.3 x 10 40 3.8 X 10 -37 2.6 x 10 35 2.4 X 10 -33
640 H . L. D u e t al.

TABLE 2. THE VALUES OF aAl FOR THE FORMATIONOF A l 2 0 3 BETWEEN 6 5 0 AND 8 5 0 ° C AT

THE TiO2/suBsTRATE INTERFACE

650°C 700°C 750°C 800°C 850°C

aAl 6.1 × 10 - 8 1.7 × 10 - 7 3.1 X 10 - 6 1.2 X 10 - 5 4.5 X 10 -5

titanium activity, amin Ti. Although no exact values for aluminium and titanium
activities in this alloy are openly available, the reported values of aA~ = 2.8 × 10-4
and aTi -----0.81 for Ti-12.6 AI alloy at 800°C 15 are used as reference points. Clearly,
the aAl is about four orders of magnitude smaller than aTi in this binary alloy whose
aluminium content is somewhat higher than that in the Ti--6AI--4V alloy. From this it
can be concluded that TiO2 would preferentially develop as soon as the Ti-6A1-4V
alloy is exposed. Once a thin TiO2 film is formed, the substrate would be separated
from its environment. ThepO2 at the interface of the TiO2 layer and substrate would
decrease considerably to a value approaching that of the dissociation partial pressure
of TiO2, which is equal to the calculated value of amin Ti (see Table 1). It is apparent
that at such a low pO2, the minimum aluminium activities required to form A1203 at
various reaction temperatures must be relatively high, as shown in Table 2, assuming
unity for aTi in Ti-6A1--4V alloy. The calculated results indicate that reaction (3) lies
almost in an equilibrium state at the TiO2/substrate interface. Furthermore, it is
reported l° that addition of vanadium suppresses the formation of an alumina barrier,
which implies that vanadium reduces the aluminium activity in the Ti-6AI-4V alloy.
Therefore A1203 would be unlikely to develop at the TiO2/substrate interface. Also
it is likely that other oxides, such as TiO with varying stoichiometries and possibly
Ti203, formed. It is believed that aluminium may dissolve in these oxides and reduce
the AI activity at the interface. This explains the fact that an alumina layer was never
observed at the oxide/substrate interface.
At the gas/oxide scale interface, the near atmospheric oxygen partial pressure
substantially reduced the minimum aluminium activity required for the formation of
A1203 as shown in Table 1. It is apparent that aluminium and titanium would diffuse
outward from the substrate to the external gas/oxide interface. According to the
calculated minimum values of aluminium and titanium activities at this interface,
titanium oxide is still the favoured reaction product. On the other hand, oxygen
species would diffuse inward to the oxide/substrate interface and react with titanium
to form TiO2 and increase the thickness of the TiO2 layer. Consequently, titanium
would be trapped at the oxide/substrate interface, thus allowing more aluminium to
diffuse outwards. Therefore, it would be more kinetically favourable for an A1203
layer to form at the gas/oxide interface.
When this double-layered oxide scale was established, the outer A1203 layer
developed by outward diffusion of aluminium species, whilst the inner layer of TiO2
grew by oxygen ingress. With the growth of this double-layered oxide scale, the issue
of how the oxide scale and substrate would keep good contact needs to be addressed.
At the initial stages of oxidation, it is possible to maintain contact between the oxide
scale and substrate by plastic flow of the oxide scale.16 Since the plasticity of this
oxide scale is limited, cracks would form between the oxide scale and substrate once
a critical thickness of the oxide scale is exceeded. The stress caused by the mismatch
in expansion coefficients between the oxide scale and substrate can be released by
 Air oxidation behaviour of Ti-6A1-4V 641

~203

Substrate Substrate

(a) Formation of T i O z layer (b) Nucleation of AI20~and

thickening of TiO2 layer

Crack Crack

Substrate
Crack

Substrate 7
J
(c) Formation of AI203 layer (d) Subsequent AI:O3 and
and occurrence of crack TiO2 layering

FIc. 8. Schematic illustrating the mechanism controlling air oxidation of Ti-6A1-4V alloy
between 650 and 850°C.

cracking initially at the edges of the specimen and then expanding progressively
through the entire specimen surface. The occurrence of the detachment at the scale/
substrate interface would make outward diffusion of aluminium and titanium
difficult and their transport rate would decrease. The inner-surface of the TiO 2 layer
would be no longer saturated with Ti species. In contrast, the oxygen species would
still diffuse inward and as a result, the partial pressure of oxygen in the crack would
increase significantly and the equilibrium state of the O-TiO2-Ti system would no
longer exist. On the substrate side the establishment of high oxygen partial pressure
in the crack would produce conditions favourable for the formation of the second
TiO 2 layer. This layer would again separate the substrate from its environment in the
crack where the conditions might be similar to the bulk atmosphere. Aluminium
from the substrate would again diffuse outward and form the second Al203 layer on
the second TiO2 layer in the crack. The oxidation mechanism of the Ti-6AI-4V alloy
is schematically described in Fig. 8. A secondary process which brings about the
partial filling of the crack with the reaction products would prevent the complete
disengagement of the initially formed oxide scale and the substrate. Some cracks
between the second alumina layer and the first TiO 2 layer are still visible, as indicated
in Fig. 6.
The above hypothesis would also account for the observed increase in the number
of alternating Ai203 and TiO2 layers with increasing exposure time. Increasing the
experimental temperature would enhance the diffusion process for both oxygen and
642 H.L. Du et al.

s u b s t r a t e e l e m e n t s , a n d c o n s e q u e n t l y , e n h a n c e the cyclic growth of A I 2 0 3 a n d T i O 2

layers, thus i n c r e a s i n g the n u m b e r of layers.

CONCLUSIONS
1. A i r o x i d a t i o n of T i - 6 A I - 4 V alloy followed a p a r a b o l i c rate law at 650 a n d
700°C after a logarithmic p e r i o d . A b o v e 700°C this alloy oxidised according to
l i n e a r - p a r a b o l i c kinetics. A t 850°C, o x i d a t i o n of the alloy followed a p a r a b o l i c rate
law again after 50 h l i n e a r p a r a b o h c o x i d a t i o n .
2. T h e oxide scale d e v e l o p e d o n the T i - 6 A 1 - 4 V alloy consisted of a l t e r n a t i n g
layers of A l 2 0 3 a n d T i O > T h e n u m b e r of the A1203 a n d TiO2 layers i n c r e a s e d with
i n c r e a s i n g e x p o s u r e time a n d t e m p e r a t u r e . T h e e x t e r n a l gas/oxide interface was
always o c c u p i e d by an A l 2 0 3 layer a n d TiO2 was always identified at the oxide/
s u b s t r a t e interface.

Acknowledgement--Funding of Dr H. L. Du, as a Research Fellow, at the University of Northumbria at

Newcastle, and Dr D. B. Lewis, as Senior Research Fellow, at SheffieldHallam University, by the Science
and Engineering Research Council's Rolling Grant in Surface Engineering is gratefully acknowledged.

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