M A TE RI A L S C H A RAC TE RI ZA T ION 6 0 ( 2 00 9 ) 1 2 6 3–1 2 6 7

a v a i l a b l e a t w w w. s c i e n c e d i r e c t . c o m

w w w. e l s e v i e r. c o m / l o c a t e / m a t c h a r

Al2O3/Ti6Al4V diffusion bonding joints using Ag–Cu interlayer

M.I. Barrena⁎, L. Matesanz, J.M.Gómez de Salazar

Department of Material Science, Faculty of Chemistry, Complutense University of Madrid 28040 Madrid, Spain

AR TIC LE D ATA ABSTR ACT

Article history: Ceramic materials, such us alumina, are widely used for wear resistant and industrial
Received 3 February 2009 components as in aircraft applications. On the other hand, Ti6Al4V is commonly used for
Received in revised form 8 May 2009 aeronautical applications, due to its superplasticity, low weight and high mechanical
Accepted 14 May 2009 resistance but has poor wear resistance because of its low resistance to plastic shearing. For
these reasons numerous techniques have been developed to improve its wear resistance
Keywords: including joining to ceramic materials. Ceramics and alloys can be joined by several
Diffusion bonding different processes and the use of an interlayer can further facilitate this process. In the
Interlayer present work Al2O3 and Ti6Al4V alloy have been diffusion bonded using a (Ag–Cu) interlayer.
Alumina Identification of intermetallic phases formed within the bonded region enables the
Microstructure mechanical behaviour of the joints to be explained. These intermetallic phases are related
Mechanical properties to the bonding conditions applied (750 °C, 3 MPa with bonding times varied from 10 to
60 min).
© 2009 Elsevier Inc. All rights reserved.

1. Introduction diffusion bonding process as a result of the different thermal

The joining of ceramics to structural alloys has received much
attention in recent years because of its potentially attractive
properties. These materials can be joined by several different
processes, such as diffusion bonding, the use of a beneficial
interlayer, transient liquid phase (TLP), brazing and friction
welding [1–7].
In actual fact, Ti6Al4V alloy is widely used for aeronautical
applications, due to its superplasticity, low weight and high
mechanical resistance [8]. However, it has a poor wear
resistance because of its low resistance to plastic shearing
[9,10]. For these reasons numerous techniques have been
developed to improve the wear resistance of Ti6Al4V alloy [11].
The activity of Ti in Ag–Cu brazing alloys is increased with a
high Ag/Cu ratio [12]. Generally, intermetallic compounds
have been regarded as brittle phase due to their low toughness
and ductility; hence their formation has been avoided during
processing. However, the possible formation of intermetallic
compounds of Ti–Cu system [13,14] is a good solution to
forming a stable interface in the joint between ceramic and
metal. It should be noted that residual stress arises during the
expansion coefficients between alumina (5.5 · 10− 6 K− 1) and
Ti6Al4V alloy (9 · 10− 6 K− 1). This effect can be minimized using
a soft interlayer. Mechanical properties of the joint will be
influenced by both the microstructure within the diffusion
zone and the nature of the intermetallic compounds formed
during the bonding process [15–17]. Moreover, the lack of
continuity in the joint will promote void formation, which will
lower the strength of the diffusion bonded joint.
2. Experimental Procedure
The ceramic material used in this study was alumina (99.1%
Al2O3) in the form of rods (10 mm diameter and 25 mm length).
Ti6Al4V (AMS 4911) alloy (in the form of sheets
25 mm × 25 mm × 2 mm) presents a biphasic α + β microstruc-
ture and a nominal composition (wt.%) of 5.5Al, 3.5V and
balanced Ti. Eutectic Ag–Cu alloy film (72 wt.% Ag, 28 wt.% Cu),
of 60 µm thick, was used as a bonding interlayer. This
interlayer was obtained on the Al2O3 surface, by electron
beam evaporation in a Pfeiffer Vacuum Classic 250, using an

⁎ Corresponding author. Tel.: +34 1 3944351; fax: +34 1 3944357.

E-mail address: ibarrena@quim.ucm.es (M.I. Barrena).

1044-5803/$ – see front matter © 2009 Elsevier Inc. All rights reserved.
doi:10.1016/j.matchar.2009.05.007
1264 M A TE RI A L S C H A RAC TE RI ZA T ION 6 0 ( 2 00 9 ) 1 2 6 3–1 2 6 7

Fig. 2 – Mechanical arrangement for shear tests of the

Ti6Al4V/Al2O3 bonded joints.

Philips X'pert PRO, with 45 kV, 40 mA, λCu = 1.5418 Å, and a

windows of 10 μm.
Fig. 1 – (a) Schematic representation of the sample assembly; Mechanical properties were evaluated by shear and micro-
and (b) thermal diffusion bonding cycle used in the joint hardness tests. A universal testing equipment (10 Tn) Servosis
Ti6Al4V/Al2O3. MEM-10 was used for shear tests, using the arrangement
shown in Fig. 2. The microhardness test was carried out in a
MHP microhardness tester mounting in a Carl-Zeiss Optical
Microscope using a magnification of 400 and applying loads of
accelerating voltage of 6 kV and a vacuum of 104 Pa. In order to 10 g.
obtain a homogeneous eutectic alloy, it was necessary to carry
out further heat treatment in a vacuum furnace at 600 °C
for 3 h. 3. Results and Discussion
Alumina and Ti6Al4V were ground with emery paper to
obtain a surface roughness (Ra) between 0.18 and 0.24 μm. A The bonding temperature was selected to be under the solidus
schematic representation of the test assembly before the line of the bonding interlayer alloy phase diagram. The
diffusion welding is shown in Fig. 1a. These samples were bonding temperature governs the formation of phases due to
then introduced into a vacuum furnace (10− 3–10− 2 Pa). In this diffusion processes in the bond region. According to the Ag–
paper bonding temperature and load were set at 750 °C Ti–Cu phase diagram, the phases which can be originated
and 3 MPa, respectively, for bonding times from 10 to 60 min during the interdiffusion process are shown in Fig. 3.
(Fig. 1b). As a consequence of the diffusion processes and phase
For metallographic examination, the bonded joints were formations during the solid state bonding process, the Al2O3/
sectioned transversely to the bond line, grounded, polished AgCu/Ti6Al4V bonded joints exhibit the formation of new
and etched with a Keller's reagent. The microstructure was
evaluated by scanning electron microscopy (SEM-JEOL JSM
6400) equipped with a Link EDX microanalysis and by
transmission electron microscopy (TEM) (JEOL 300F). The
phases originated during the diffusion process can be
identified using microanalysis tests. The composition (wt.%)
of these phases was obtained as an arithmetic mean of five
tests. Preparation of specimens for TEM was carried out as
follows: cutting the joints in 0.5 mm thick slices using a
diamond disc; mechanical grinding of the slices on SiC paper
(1200 grade, in ethylene glycol down to 100 μm; ultrasonic
cutting of a 3 mm diameter disc; mechanical thinning of the
disk with 2000 and 4000 grade emery paper down 50 μm;
dimple in the centre of the disc using 3 mm and 1 mm
diamond pastes to reduce minimum sample thickness to a
range of 0.10–0.15 mm; and ion milling using an Ar+ ion beam
with a cooling system and a gun voltage of 5 kV and incident
angle of 15° with thinning times of 10–15 h. X-ray Diffraction
(XRD) analyses were carried out using a microdiffractometer Fig. 3 – Ag–Cu–Ti ternary diagram.
 M A TE RI A L S C H A RAC TE RI ZA T ION 6 0 ( 2 00 9 ) 1 2 6 3–1 2 6 7 1265

Fig. 4 – SEM images of Ti6Al4V/Al2O3 interface microstructure at bonding temperature of 750 °C for (a) 10 min; (b) 20 min;
(c) 30 min; and (d) 60 min.

intermetallics and diffusion layers. The number of these layers, The reaction on the surface of the materials begins with the
their thickness and composition will change according to the diffusion processes from the Ag–Cu interlayer with the surface
bonding conditions such as time (10 to 60 min), temperature and to the Ti6Al4V alloy. The phase that appears near Ti6Al4V alloy
pressure applied during the bonding processes. is a narrow reaction zone, constituted by the eutectoid Cu–Ti
In this case, the reactivity of the interlayer with the ceramic system (marked as A layer in Fig. 4), which is composed by the α-
and metal surfaces leads to the formation of reaction products Ti phase and the η-Ti2Cu phase. Close to this layer appears a
at the interface, due to the high solubility (2 wt.%) of titanium narrow layer constituting principally of the η phase (layer B) and
(Ti) in silver (Ag) and Ag in Ti (8 wt.%). However, copper the next layer is the ζ-TiCu phase (layer C). Layer D constitutes a
solubility in titanium is about 0.9 wt.%, and Ti in Cu is about mixture of phases ζ + Ag+ λ-Ti3Cu4. A silver rich layer, Ag(Cu,Ti),
2.5 wt.%. The reactivity of element in the interface can be appears (layer E) close to this layer, which is formed by Ag (white
corroborated by comparing the microstructures obtained for phase) and Ti and Cu in solid solution (dark phase).
bonding times of 10 min (Fig. 4a), 20 min (Fig. 4b), 30 min From the alumina surface, the reaction interface is a
(Fig. 4c) and 60 min (Fig. 4d). Different titanium–copper phases complex layer where layer F (ε-Ti2Cu3 and γ-TiCu4), marked
can be identified as diffusion layers formed between Ti6Al4V
and alumina (Table 1), their thickness depending on the
bonding time used (Table 2). Table 2 – Thickness and phases identified in the diffusion
layers.
Layer Phases Thickness of diffusion bonding
Table 1 – Composition in wt.% of different titanium–copper layer (μm)
phases analysed.
10 min 20 min 30 min 60 min
Phases Composition in wt.%
A αTi + η (Ti2Cu) 9 15 30 52
Ag Cu Ti
B Ag + η (Ti2Cu) 9 3 2 –
Ag + η (Ti2Cu) 5.0 32.0 63.0 C Ag + ζ (TiCu) – 14 12 –
Ag + ζ (TiCu) 4.5 54.0 41.5 D Ag + λ (Ti3Cu4) – 5 – –
Ag + λ (Ti3Cu4) 3.0 60.0 37.0 E Ag(Cu,Ti) 40 20 10 –
Ag + ε (Ti2Cu3) 4.5 65.5 31.0 F Ag + ε (Ti2Cu3) + 2 3 6 8
Ag + γ (TiCu4) 2.5 81.5 15.5 γ (TiCu4)
1266 M A TE RI A L S C H A RAC TE RI ZA T ION 6 0 ( 2 00 9 ) 1 2 6 3–1 2 6 7

Fig. 5 – TEM images of (a) interface between the F layer and Al2O3 base material where the Cu3TiO4 phase (marked as AF) coexists
with the Cu2Ti4O phase (marked as BF); and (b) detail of the Cu2Ti4O phase morphology.

in Fig. 4, coexists with a layer with a thickness of 1.5 μm. This
last layer studied by TEM (Fig. 5), is made up of two phases, the
Cu3TiO4 phase with hexagonal structure and lattice spacing of
a = 3.035 Å and c = 11,440 Å (marked as AF in Fig. 5a) and
Cu2Ti4O phase (marked as BF in Fig. 5a) with cubic structure
and lattice spacing of a = 11,490 Å (Fig. 5b). In the ceramic
interface, the reaction of copper titanium compounds with
oxygen is possible [18].
The microhardness values obtained for reaction zone
(Fig. 6) are directly related to the composition, thickness and
number of diffusion layers generated. The low microhardness
values are associated with the interlayer zone rich in silver.
The microhardness values increase as the base materials
(Ti6Al4V and Al2O3) are approached, due to the formation of
Ti–Cu system phases associated to the diffusion mechanisms
that take place in the diffusion bonding interface.
When the shear tests of the bonded samples were carried
out (Fig. 7), it was observed that the strength of the joints
increases with the bonding time. However, when the bonding
time is longer than 60 min the shear value decreases. This fact
is associated with the presence of brittle phases, as Cu3TiO4
and Cu2Ti4O, in the discontinuous interlayer/Al2O3 bonded
interface. The analysis of fracture surfaces obtained after
shear tests shows that all alumina joints broke but not at the
joint interface, and that cracks began close to the bonding
interface, except in the samples bonded for 60 min, which
broke through the F layer due to the formation of oxides
(Fig. 8). The brittle break takes place by both transgranular and
intergranular fracture mechanisms (Fig. 9) when the fracture
occurs in the alumina. This allows us to determine that the
different layers originated during the diffusion bonding
present more ductility than the Al2O3 base material.
4. Conclusions
Solid-state diffusion bonding was carried out between Ti6Al4V
and Al2O3 using a 60 μm Ag–Cu interlayer. A high quality joint
is guaranteed when bonding conditions of 750 °C for 10–30 min
under 3 MPa uniaxial load in vacuum were applied. Long
bonding times promote oxide formation and a discontinuous
joint interface. The joining of Ti6Al4V to Al2O3 occurred by the
formation of a homogeneous diffusion interface on the metal
side of the joint. The diffusion mechanism's origin is different

Fig. 6 – Microhardness values of the bonding interface Fig. 7 – Shear strength vs. bonding time, at a bonding
Ti6Al4V/Al2O3. temperature of 750 °C.
 M A TE RI A L S C H A RAC TE RI ZA T ION 6 0 ( 2 00 9 ) 1 2 6 3–1 2 6 7
Fig. 8 – XRD analysis of fracture surface of Ti6Al4V/Al2O3 joint
obtained at a bonding temperature of 750 °C for 60 min.
Fig. 9 – SEM image of the fracture surface into the alumina, after
the shear test (a) transgranular fracture and (b) intergranular
fracture.
from the diffusion layers which are composed of combina-
tions of silver and intermetallic phases of the Ti–Cu system.
The mechanical properties will therefore depend on the
thickness and composition of these diffusion layers which
will be modified when the bonding time varies.
1267
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