International Journal of Adhesion & Adhesives 29 (2009) 259267

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International Journal of Adhesion & Adhesives

journal homepage: www.elsevier.com/locate/ijadhadh

High-performance nanoadhesive bonding of titanium for aerospace and

space applications
S. Bhowmik a,!, R. Benedictus a, J.A. Poulis a, H.W. Bonin b, V.T. Bui b
a
b

Faculty of Aerospace Engineering, Delft University of Technology, Kluyverweg 1, 2629 HS Delft, The Netherlands
Department of Chemistry and Chemical Engineering, Royal Military College of Canada, Kingston, Ontario, Canada K7K 7B4

a r t i c l e in fo

abstract

Article history:
Accepted 10 July 2008
Available online 25 July 2008

In this investigation, attempts are made to prepare high-performance nanoadhesive bonding of

titanium for its essential applications to aviation and space. The high-performance nanoadhesive is
prepared by dispersing silicate nanoparticles into the ultra-high-temperature-resistant epoxy adhesive
at 10 wt% ratio with the matrix adhesive followed by modification of the nanoadhesive after curing
under high-energy radiation for 6 h in the pool of SLOWPOKE-2 nuclear reactor with a dose rate of
37 kGy/h to promote crosslink into the adhesive. Prior to bonding, the surfaces of the titanium sheets are
mechanically polished by wire brushing, ultrasonically cleaned by acetone and thereafter the titanium
sheets are modified by plasma ion implantation using plasma nitriding. The titanium surface is
characterized by X-ray photoelectron spectroscopy (XPS). The thermal characteristics of the epoxy
adhesive and the high-performance nanoadhesive are carried out by thermal gravimetric analysis (TGA).
The TGA studies clearly shows that for the basic adhesive there is a weight loss of the adhesive, however,
in the case of epoxysilicate nanoadhesive, there is almost 100% retention of weight of the adhesive,
when the adhesive is heated up to 350 1C. Lap shear tensile strength of the joint increases considerably,
when the titanium surface is modified by plasma-nitriding implantation. There is a further massive
increase in joint strength, when the plasma-nitriding implanted titanium joint is prepared by
nanosilicateepoxy adhesive and further modification of the adhesive joint under high-energy radiation
results a further significant increase in joint strength. In order to simulate with aviation and space
climatic conditions, the joints are separately exposed to cryogenic (!196 1C) and elevated temperature
(+300 1C) for 100 h and thermal fatigue tests of the joints are carried out under 10 cycles by exposing the
joint for 2 h under the above temperatures. When the joint completely kept at ambient condition and
the joint strength compared with those joints exposed to aviation and space climatic conditions, it is
observed that the joint could retain 95% of the joint strength. Finally, to understand the behavior of the
high-performance silicateepoxy nanoadhesive bonding of titanium, the fractured surfaces of the joints
are examined by scanning electron microscope.
& 2008 Elsevier Ltd. All rights reserved.

Keywords:
High temperature adhesives
Titanium and alloys
Durability

1. Introduction
The use of titanium for structural elements of aerospace and
spacecraft become extensive during the early Mercury and Apollo
program, and even in the present days, titanium alloys continue to
be widely used in aerospace and space applications. In addition to
manned spacecrafts, titanium alloys are extensively employed in
solid rocket booster cases, guidance control pressure vessels and a
wide variety of applications demanding lightweight and reliability
[1]. The aerospace industry is also a larger market for titanium
products primarily due to the exceptional strength-to-weight ratio,
and high resistance to elevated temperatures and corrosion [2].

! Corresponding author. Tel.: +3115 27 84186; fax: +3115 27 81151.

E-mail address: S.Bhowmik@TUDelft.Nl (S. Bhowmik).

0143-7496/$ - see front matter & 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijadhadh.2008.07.002

Often in the fabrication processes, titanium sheets are joined by

adhesive rather than by welding or riveting. The acceptance of
adhesives as a high-performance engineering material has grown
steadily in the last few decades [2,3]. Adhesives contribute highly
to structural integrity, ease of manufacturing, enhanced performance, improved safety and cost and time savings. The reasons for
this are numerous and include the continuity of the adhesive
bond. Therefore, upon loading, there is a more uniform distribution of stresses over the bonded area [3,4]. However, for
improving the performance of adhesive bonding of titanium for
aerospace and space climatic conditions, it is necessary to modify
the surface of titanium [4]. It is established that diffusion of
nitrogen atoms to crystal lattice of a metal surface is known as
nitriding and that essentially improves corrosion resistance of the
metal leading to performance of the metal under aerospace and
space climatic conditions [5].

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However, the main problem with the application of adhesive

for spacecraft and supersonic and hypersonic aircraft is high
temperatures. This is caused by the aerodynamic friction heating
of the structure as it moves through the air. The temperatures vary
from approximately 50 1C at Mach 1, 200 1C at Mach 2, 450 1C at
Mach 3 and to above 800 1C at Mach 3.5 [4]. Therefore, the use of
basic organic resins as adhesives become very difficult above
Mach numbers of 2 [4] and consequently, high-temperatureresistant adhesives are obviously required.
Presently, investigation on polymerclay nanocomposite has
become a very important research area, because it is established
that thermal and mechanical properties of polymersilicate
nanocomposite are far superior to those of conventional polymer
or polymeric microcomposites [68]. Therefore, with this
principle, high-performance adhesive can be prepared by dispersing silicate nanopowder to matrix adhesive and that could
open a new horizon on thermomechanical properties of adhesive
bonding.
Based on these considerations, in this investigation, the surface
modification of titanium is carried out by plasma ion implantation
through plasma nitriding followed by joining of titanium sheets
with an ultra-high-temperature-resistant epoxy adhesive (DURALCO 4703) and by dispersing silicate nanopowder into the ultrahigh-temperature-resistant epoxy adhesive at 10 wt% ratio with
the matrix adhesive followed by modification of the nanoadhesive
after curing under high-energy radiation for 6 h in the pool of
SLOWPOKE-2 nuclear reactor with a dose rate of 37 kGy/h in order
to essentially increase the crosslink density within the nanoadhesive resulting in much improved thermomechanical properties
of the adhesive [9]. The plasma-nitrided titanium surface is
characterized by X-ray photoelectron spectroscopy (XPS). The
physicothermal characteristics of the basic ultra-high-temperature-resistant epoxy adhesive and the high-performance ultrahigh-temperature-resistant silicate nanoadhesive is carried out by
thermal gravimetric analysis (TGA). Tensile lap shear tests of the
adhesive joints have been carried out to determine the effects of
these environments on the joint strength. Finally, in order to
understand the failure mode of the joints, the fractured surfaces of
the joints after failure under tensile lap shear tests have been
examined under scanning electron microscope (SEM).

2. Experimental
2.1. Materials
In this investigation titanium sheets of grade 2 (ASTM F 67-95)
were used for preparation of the adhesive joints. The elemental
composition of the titanium sheet was analyzed by neutron
activation analysis (NAA), as reported in Table 1. Recently
developed ultra-high-temperature-resistant epoxy adhesive, DURALCO 4703, and which is difunctional in nature, manufactured by
Cotronics Corp. Brooklyn, NY, USA of service temperature ranging
from !260 to +350 1C, was used to join the titanium sheets. The
mixing ratio of resin to hardener, curing temperature and time of
this adhesive are: 1:0.22, 120 1C and 4 h, respectively, as given by
the manufacturer for the best condition. Unmodified silicate
nanopowder of 50 nm of particle size, manufactured by Glassven,
La Victoria, Aragua 2121 United States was used as dispersing
Table 1
Elemental composition of the titanium sheet
Al

Cl

Cu

Mn

Na

Ti

2.13%

0.54%

0.35%

0.17%

0.33%

2.00%

94.48%

nanoparticles into the adhesive and thereafter, and in all the cases
degassing of the adhesive was carried out in a vacuum chamber
under a pressure of 100 Pa.
2.2. Surface modification and surface characterization of titanium
Prior to joining, the surfaces of the titanium sheets were
mechanically polished by wire brushing, according to ASTM D 897
standard, cleaned with isopropanol and then modified by plasmanitriding implantation in order to alter the chemical feature of
the titanium surface leading to substantial improvement of the
titanium surface against corrosion. Plasma nitriding is carried
out through glow discharge under nitrogen as process gas. The
apparatus consists of a vacuum vessel, a gas handling system and
a high-voltage power supply. First, the vacuum vessel is evacuated
using a mechanical pump to a base pressure of 10!3 Pa and
nitrogen gas is introduced into the vacuum chamber through a
leak valve and filled up to 100 Pa. A high voltage is established
between the grounded vessel and the sample to be nitrided, which
is at the cathode potential. In this investigation, the surface of the
titanium was modified under 120 min of exposure under 150 W of
power. The schematic diagram of the plasma-nitriding reactor is
shown in Fig. 1.
Surface characteristics of unmodified titanium as well as on
modified titanium surfaces are carried out by XPS. The XPS was
carried out using an SSLSSX-100 X-ray photoelectron spectrometer at Ecole Polytechnique, Canada, by using monochromatised
AlKa X-ray source, operated at a power of 200 W. The base
pressure in the sample chamber during analysis was 2 " 10!10 Pa.
Survey spectra were obtained using a pass energy of 58.7 eV and
during the analysis, the electron take-off angle was set at 451 and
the acquisition time was 6 min.
2.3. Physicothermal characterization of adhesive
Physicothermal characteristics of the basic ultra-high-temperature-resistant epoxy adhesive and the silicate nanopowder
dispersed ultra-high-temperature-resistant adhesive were carried
out by TGA. TGA thermograms were obtained on a Universal V2
5H TA Instruments equipment, under a nitrogen atmosphere at a
heating rate of 10 1C/min, and scanned from 25 to 500 1C. The
cured adhesive samples were cut in the shape of thin discs. The
samples ranged between 8 and 12 mg in weight and were placed
in platinum sample pans under a continuous nitrogen flow of
200 mL/min.
2.4. Preparation of the adhesive joint
The tensile lap shear test samples are prepared using titanium
sheets of dimensions 125 " 25 " 6 mm3 by applying the ultrahigh-temperature epoxy adhesive at an overlap length of 25 mm.
Any excess adhesive present at the interface was expelled out by
pressing the joint under a load of 10 kg. The tensile lap shear test
is performed according to the ASTM D 5868-95 standard, using an
Instron Universal Testing Machine under a load cell of 10 kN at a
test speed of 5 mm/min at room temperature.
The following four types of adhesive tensile lap joints were
tested:
(i) The basic ultra-high-temperature-resistant epoxy adhesive
lap joints of titanium-to-titanium was fabricated and cured at
120 1C for 4 h.
(ii) The basic ultra-high-temperature-resistant epoxy adhesive
lap joints of titanium-to-titanium irradiated for 6 h to
SLOWPOKE-2 nuclear reactor with a dose rate of 37 kGy/h.

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VACUUM VESSEL

LEAK VALVE

VALVE
TO PUMP

SAMPLE
SAMPLE HOLDER

GAS
REGULATOR
THERMOCOUPLE

HIGH VOLTAGE
OPTPISOLATOR

NITRIDING
GAS
MIXTURE

PULSE POWER
SUPPLY
MICROCOMPUTER

Fig. 1. Schematic diagram of the plasma-nitriding reactor.

(iii) Silicate nanopowder with 10 wt% ratio was dispersed into the
above epoxy adhesive with a mixing through mechanical
stirrer and then the adhesive lap joints of titanium-totitanium was fabricated and cured at 120 1C for 4 h.
(iv) Silicate nanopowder with 10 wt% ratio was dispersed into the
above epoxy adhesive with a mixing through mechanical
stirrer and then the adhesive lap joints of titanium-totitanium was fabricated and cured at 120 1C for 4 h, and after
curing the joints were irradiated for 6 h under SLOWPOKE-2
nuclear reactor with a dose rate of 37 kGy/h, when the reactor
is at steady-state half-power operation of 10 kW (thermal)
[9]. At this site, the radiation components contributing to this
dose rate are a combination of 1% neutron, 3% proton, 9%
gamma and 87% electron radiation [9]. The sample holder
used for the irradiation was an aluminum sector-shaped box
designed to fit snugly against the reactor vessel. The holder
could accommodate seven samples, which were all well
covered by a waterproof tape to avoid all contact with water
in the reactor pool. The sample holder was held in position in
the reactor pool by a positioning device called the elevator,
designed to position and maintain samples at a repeatable
irradiation site at mid-reactor plane and against the reactor
vessel. The schematic diagram of the SLOWPOKE-2 nuclear
reactor is shown in Fig. 2.

2.6. Microscopic studies of adhesives and fractography

For each set of conditions, seven joints are tested and the mean
value is reported in the result.

3.2. TGA and SEM studies on basic adhesive and nanoadhesive

2.5. Durability test

According to lap shear tensile test datas of the above
four joints, durability of the adhesive joints was carried out
on the best joint. The joints are separately exposed to cryogenic
(!196 1C) for 100 h and elevated temperature (+300 1C) for
100 h and thermal fatigue tests of the joints are carried out less
than 10 cycles by exposing the joint for 2 h under the above
temperatures.
For each set of environmental conditions, seven joints are
tested and the mean value is reported in the result.

Microscopic studies of basic epoxy adhesive and silicate

nanopowder dispersed epoxy adhesive is carried out under SEM.
The fractured surfaces of the adhesive joints prior to and after
environmental exposure are also examined under SEM. Typical
features of the fractured surfaces are photographed.

3. Results
3.1. XPS studies on the titanium surface
The XPS studies on the titanium surface have been carried out
for the as-received titanium surface and those titanium modified
by plasma-nitriding implantation. XPS wide scan spectra of the
as-received titanium surface shows the C 1s peak, O 1s peak, a
concentration of N 1s and Ti 2p peaks, as shown in Fig. 3.
However, due to the surface modification of titanium under
plasma-nitriding implantation, the chemical constituents of the
titanium surface changes as evident from Fig. 4. In this case, the
titanium surface shows significant increase in O 1s and Ti 2p
peaks and a small increase in N 1s peak, as shown in Fig. 4, and
data are given in Tables 2 and 3.

The results from the TGA on physicothermal characteristics of

the epoxy adhesive and the silicate nanoepoxy adhesive are
shown in Figs. 5 and 6, respectively. The peak of the TGA,
especially the second peak represents, the phase changing
temperature followed by severe weight loss of the adhesive
corresponding to each stage in the whole process. It is found that
the degradation of the basic epoxy adhesive is a two-stage
process: a relatively short stage with a very small percent of
weight loss beginning at about 125 1C, followed by about 8% of
weight loss up to 350 1C, attributed a degradation of the adhesive
over the ranges of temperatures up to 350 1C and thereafter, there
is a massive degradation of the adhesive. However, for the
silicateepoxy nanoadhesive, degradation of the adhesive occurs

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CENTRAL CONTROL
ROD

SHIM TRAY

INSTRUMENT
SOCKET
BERYLLIUM
SHIMS

SMALL
SAMPLE
IRRADIATION
TUBE

CRITICAL
ASSEMBLY
TOP PLATE
BERYLLIUM
ANNULUS

REACTOR
VESSEL

LARGE
SAMPLE
IRRADIATION
TUBE

BOTTOM
ANNULAR
PLATE

CORE

PLATFORM
LOWER BERYLLIUM REFLECTOR
Fig. 2. Schematic diagram of SLOWPOKE-2 nuclear reactor.

2.20 10+05

O1s

2.00 10+05
1.80 10+05
1.60 10+05
Ti2p

1.20 10+05
1.00 10+05

C1s

8.00 10+04
6.00 10+04

N1s

Counts / s

1.40 10+05

4.00 10+04
2.00 10+04
0.00 10+04
100

1000

900

800

700
600
500
400
Binding Energy (eV)

Fig. 3. XPS of unmodified titanium surface.

300

200

100

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O1s

4.00 10+05

Ti2p

2.00 10+05

0.00 10+05
100

N1s

1.00 10+05

1000

900

800

700
600
500
400
Binding Energy (eV)

C1s

Counts / s

3.00 10+05

300

200

100

Fig. 4. XPS of plasma-nitrided titanium surface.

Table 2
XPS of untreated titanium surface
Name

Peak binding energy

Height CPS

FWHM (eV)

Area (P) CPS (eV)

Area (N)

At%

SF

O 1s
Ti 2p
N 1s
C 1s

531.00
459.00
397.00
286.00

63,833.04
45,528.08
3625.09
27,079.37

2.27
3.72
2.24
2.52

303,337.12
305,014.42
7980.99
124,146.54

0.11
0.04
0.00
0.11

43.04
15.09
1.63
40.24

N
N
N
N

Y
Y
Y
Y

0.660
1.800
0.420
0.250

Table 3
XPS of plasma-nitrided titanium surface
Name

Peak binding energy

Height CPS

FWHM (eV)

Area (P) CPS (eV)

Area (N)

At%

SF

O 1s
Ti 2p
N 1s
C 1s

531.00
459.00
397.00
286.00

207,304.24
160,071.18
19,298.18
18,693.21

2.04
2.64
2.50
3.61

589,130.70
675,111.51
48,124.88
57,135.11

0.22
0.09
0.03
0.05

57.51
22.98
6.67
12.74

N
N
N
N

Y
Y
Y
Y

0.660
1.800
0.420
0.250

400

500

110

110

100
Weight (%)

Weight (%)

100

90

80

80

70

90

70
0

100

200
300
Temperature (C)

400

500

Universal V2.5H TA Instruments

Fig. 5. TGA plot of the basic high-temperature-resistant epoxy adhesive.

100

200

300

Temperature (C)
Universal V2.5H TA Instruments
Fig. 6. TGA plot of the high-temperature-resistant epoxy adhesive when silicate
nanopowder dispersed into the adhesive in 10 wt% ratio.

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30

LAP SHEAR TENSILE STRENGTH (MPa)

Unmodified Titanium
Plasma Nitrided Titanium
25

20

15

10

0
Fig. 8. Tensile lap shear strength of basic adhesive joint of unmodified titanium
and plasma-nitrided titanium.

Fig. 7. Scanning electron micrograph showing (a) basic epoxy adhesive and
(b) epoxy adhesive when silicate nanopowder dispersed into the matrix adhesive
at 10 wt% ratio.

in one stage as steady state continues up to 350 1C, and there is no

sign of degradation of the adhesive up to 350 1C. In this case, the
percent of weight loss up to 350 1C is almost negligible as clearly
evident from Fig. 6. However, thereafter in line of the previous
case, there is a massive degradation of the adhesive. Scanning
electron micrograph of basic and nanosilicateepoxy adhesive is
shown in Fig. 7(a and b) at a magnification of 5000. The figure
clearly demonstrates a different feature, with the inclusion of
silicate nanopowder. Fig. 7(b) reveals that dispersion of silicate
nanopowder into the matrix adhesive with certain extent of
uniformity with partial agglomeration.

3.3. Lap shear tensile properties of the titaniumtitanium adhesive

joint
Fig. 8 shows the lap shear tensile properties of adhesive joints
of titanium-to-titanium, when the titanium surface has been
modified by plasma-nitriding implantation. The figure reveals
that the adhesive joint strength of the titanium-to-titanium is
10 MPa when only mechanically polished and cleaned with
isopropanol and increase to 25 MPa when the titanium surface
is further modified by plasma-nitriding implantation. In the
second case, when the basic adhesive joint of the surfacemodified titanium is exposed to high-energy radiation, joint

LAP SHEAR TENSILE STRENGTH (MPa)

70
60

Basic Epoxy Adhesive

Basic Epoxy Adhesive and Exposed to
High Energy Radiation
Nano Silicate Epoxy Adhesive
Nano Silicate Epoxy Adhesive and Exposed to
High Energy Radiation

50
40
30
20
10
0

Fig. 9. Tensile lap shear strength of adhesive joint of plasma-nitrided titanium

when the joint is prepared with basic epoxy adhesive, nanosilicate epoxy adhesive
and the nanosilicate epoxy adhesive joint further exposed to SLOWPOKE-2 nuclear
reactor for 6 h.

strength increases up to 36 MPa. It is observed that there is a

considerable increase in joint strength up to 40 MPa, when the
plasma-nitriding implanted titanium joint is prepared by nanosilicateepoxy adhesive and further modification of the adhesive
joint under high-energy radiation results a significant increase in
joint strength up to 55 MPa, as shown in Fig. 9. The joint with the
as-received titanium sheet failed partly at the interface between
the adhesive and the titanium and partly cohesively within the
adhesive, as shown in Fig. 10. But in the other three cases, the joint
fails cohesively within the adhesive and, therefore, the features
are different as evident from SEM images, as shown in Figs. 1113.

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Fig. 10. Scanning electron micrograph showing interfacial failure of adhesive joint
of unmodified titanium.

Fig. 13. Scanning electron micrograph showing cohesive failure of nanosilicate

adhesive joint of plasma-nitrided titanium when irradiated to SLOWPOKE-2
nuclear reactor for 6 h.

80

LAP SHEAR TENSILE STRENGTH (MPa)

70

Fig. 11. Scanning electron micrograph showing cohesive failure of adhesive joint of
plasma-nitrided titanium.

265

60

Joint kept at ambient condition

Joint exposed to -196C for 100 hours
Joint exposed to + 300C for 100 hours
Joint exposed to - 196C for 2 hours and + 300X
for 2 hours for 10 alternate cycles

50
40
30
20
10
0

Fig. 14. Durability under cryogenic, elevated temperature and thermal fatigue
conditions of plasma-nitrided high-performance nanosilicateepoxy adhesive
joint.

3.4. Durability of the joints under low temperature, elevated

temperature and thermal fatigue conditions
It is observed that when the best joints i.e., the type (iv) joints
are exposed to a low temperature (!196 1C) as well as an elevated
temperature (+300 1C) for 100 h, and thermal fatigue conditions
with these temperature variations under 10 cycles by exposing the
joint for 2 h at each temperature the joints could retain almost
95% of the joint strength when tests were carried out at room
temperature, as shown in Fig. 14.

4. Discussion
Fig. 12. Scanning electron micrograph showing cohesive failure of nanosilicate
adhesive joint of plasma-nitrided titanium.

The present investigation is primarily emphasized to preparing

high-performance nanoadhesive bonding of titanium, for its

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essential application to aviation and space. Therefore, considerable effort has been given to preparing high-performance
nanoadhesive by dispersing silicate nanopowder followed by its
modification under SLOWPOKE-2 nuclear reactor. Fig. 4 indicates
that due to plasma nitriding of titanium, chemical functionalities
on the titanium surface changes and that could make protective
coating on the titanium surface. Therefore, adhesive joint strength
of plasma-nitrided titanium is significantly high in comparison to
the adhesive joint strength of unmodified titanium, as shown in
Fig. 8. This is possible because the protective coating on the
titanium surface under plasma-nitriding implantation, essentially
contributed to retaining the interfacial strength of titanium to the
adhesive. The failure analysis of adhesive joints of titanium
confirms that adhesive joints of unmodified titanium joints partly
fail from titaniumadhesive interface resulting in low joint
strength. Therefore, it could be concluded that electrochemical
behavior of titanium surface could be an important factor for the
strong interface of titaniumadhesive, and that improves due to
surface modification of titanium by plasma-nitriding implantation, resulting in higher joint strength and cohesive failure from
the adhesive.
Frauchiger et al. [10] have revealed that anodic plasma
chemical processes essentially modify the chemical and morphological properties of the titanium surface. Ramani et al. [11] and
Kapczinski et al. [12] have also emphasized that surface
modification of titanium, especially by plasma sputtering and
sodium hydroxide anodization, proves beneficial in the context
of durability of the joint under severe chemical climates. It has
been reported that when titanium surfaces are modified
by plasma sputtering, chromatic acid anodizing and sodium
hydroxide anodizing, the durability of adhesive joints of titanium
improves under the wedge cleavage test [13]. In line of the present
investigation, Clearfield et al. [14] have revealed that adhesive
joints of plasma-nitrided or -anodized titanium essentially failed
cohesively within the adhesive; however, in terms of durability of
the joint, plasma nitriding is more effective. Hanawa et al. [15]
have emphasized that surface properties can also be changed
through laser or electron-beam thermal treatment without adding
or removing the material. The layer is grown electrochemically
from the bulk of the metal and modified by heat treatment, this
essentially enhancing the durability of adhesive bonding of
titanium when subjected to corrosive environments. Zinger et al.
[16] have modified titanium surface by plasma sputtering and
anodization and their observation also reveal that electrochemical
properties of titanium surface improves due to this modification.
It is well documented by various researchers that thermophysical and thermomechanical properties such as melting,
crystallization, thermal conductivity, coefficient of thermal expansion, tensile and breaking strength of epoxy as well as
polyolefins improves considerably due to incorporation of silicate
nanopowder into the matrix polymer [68]. The present investigation of nanoadhesive bonding of titanium by dispersing silicate
nanopowder to ultra-high-temperature epoxy adhesive also
shows a similar trend as there is a considerable improvement
of thermophysical and thermomechanical properties of the
adhesive as evident from Figs. 5, 6 and 9. This is because in
respect to any adhesive, the thermomechanical properties of
silicate are significantly high and, therefore, that essentially
influence the overall performance of the adhesive. However,
dispersion of silicate nanopowder with different weight ratios:
520% into the adhesive could be useful in order to investigate the
more detail influence of silicate nanopowder on the properties of
adhesive joints. In this investigation, dispersion of nanoparticles
with 10 wt% ratio with the matrix resin looks promising, although,
according to various literatures 15% are quite enough for
polymer matrix composite. However, the objective of this

investigation was to see the rationale of dispersing nanoparticles

into adhesive bonding, which is not so common. The present
investigation reveals significant improvement in adhesive bond
strength by dispersing nanoparticles; and there was agglomeration up to a certain extent. However, that extent of agglomeration
could be acceptable, as considerable improvement in adhesive
bond strength is observed.
An earlier investigation on the influence of high-energy
radiation on polymeric composite reveals that there is a
considerable increase on the mechanical strength on the polymeric composite when exposed to high-energy radiation [9],
because the exposure under high-energy radiation increases
crosslink density within the polymer, essentially affecting the
overall behavior and mechanical properties of the polymer.
Therefore, with the exposure under high-energy radiation,
mechanical properties of the adhesive joint increases significantly
because of increasing crosslink density within the adhesive [9].
A similar observation has been reported by Xu et al. [17]
and Berejka and Eberle [18] on electron-beam irradiation
on polyolefin and polymeric composite, and it states that with
the lower dose rate, mechanical properties of the polymer
increase considerably. Therefore, in this investigation, the
joints are essentially exposed to high-energy radiation, so as to
promote crosslinking within the adhesive by high-energy
radiation, and as surface-modified titanium essentially fails
cohesively within the adhesive, so it is a clear justification to
increase the joint strength up to 55 MPa with the nanoadhesive
bonding. However, in terms of space application, the joints
could be exposed to high-energy radiation from 12 to 60 h
or longer in order to see the effect of longer duration of exposure
on joint strength. When these titanium joints are exposed to
climatic conditions such as elevated as well as cryogenic
temperature related to aerospace and space conditions, the
joints could retain the joint strength of about 95% of strength of
the joint kept under ambient conditions. This could happen
because the thermal expansion and contraction coefficient
of titanium and the epoxy adhesive is different and this
difference could lead to some extent of mismatch between the
thermal expansion and contraction of titanium and the epoxy
adhesive resulting in the generation of residual stress leading to
minor decrease in the joint strength. However, this could be
within the acceptable limit in respect of aerospace and space
applications.

5. Conclusions
The present investigation has led to the following conclusions:
(i) The adhesive joint strength of titanium increases considerably from 10 to 25 MPa, when the titanium surface is
modified by plasma-nitriding implantation and the joints
failed cohesively from the adhesive when joints are prepared
by surface-modified titanium.
(ii) There is a significant increase in joint strength up to 40 MPa,
when the plasma-nitriding implanted titanium joint is
prepared by nanosilicateepoxy adhesive.
(iii) When the joints are irradiated for 6 h in the pool of
SLOWPOKE-2 nuclear reactor, for the basic adhesive, there
is an improvement of joint strength up to 36 MPa and for
nanosilicate adhesive it is up to 55 MPa.
(iv) When the joints are exposed to low as well as elevated
temperature for 100 h, and thermal fatigue conditions, the
joints could retain about 95% of their joint strength with
respect to the strength of the joint tested under ambient
condition.

ARTICLE IN PRESS
S. Bhowmik et al. / International Journal of Adhesion & Adhesives 29 (2009) 259267

Acknowledgments
The financial support provided by the Natural Science and
Engineering Research Council of Canada for carrying out this
work is gratefully acknowledged and the authors express their
thanks to Ecole Polytechnique de Montreal for the use of the
plasma-nitriding implanter equipment.
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