International Journal of Adhesion & Adhesives 70 (2016) 265–270

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International Journal of Adhesion & Adhesives

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

Effect of surface pre-treatment on surface characteristics and adhesive

bond strength of aluminium alloy
K. Leena a,n, K.K. Athira c,1, S. Bhuvaneswari b, S. Suraj a, V. Lakshmana Rao a
a
Polymers and Special Chemicals Division, Vikram Sarabhai Space Centre, Thiruvananthapuram, Kerala 695022, India
b
Analytical and Spectroscopy Division, Vikram Sarabhai Space Centre, Thiruvananthapuram, Kerala 695022, India
c
National Institute of Technology, Calicut, Kerala 673601, India

art ic l e i nf o a b s t r a c t

Article history: In this work aluminium alloy surfaces have been subjected to three different methods of surface pre-
Received 13 September 2015 treatments such as solvent degreasing, FPL (Forest Products Laboratory) etching and priming using an
Accepted 17 July 2016 epoxy based primer. The treated surfaces were evaluated for surface energy, contact angle, surface
Available online 22 July 2016
topography, surface roughness and adhesive strength characteristics. The influence of surface
Keywords: pre-treatments on the variation of polar, dispersive and total surface energy of the surfaces is addressed.
Atomic Force Microscopy C A wettability test was performed on the surfaces using an epoxy adhesive in order to assess the influence
Wettability D of the pre-treatment techniques on substrate/adhesive interaction. Theoretical work of adhesion values
Surface energy for the various pre-treated surfaces were calculated using the contact angle data and further tested
Surface roughness
experimentally by adhesive bond strength evaluation by tensile testing of a single lap aluminium-epoxy-
aluminium assembly. The method of surface pre-treatment showed a profound effect on the surface
topography and roughness by AFM. This study reveals that a combination of high surface energy and high
surface roughness of the substrate along with good wettability of the adhesive contributed to the highest
joint strength for the aluminium alloy through the FPL etching pre-treatment.
& 2016 Elsevier Ltd. All rights reserved.

1. Introduction blasting, acid / alkaline etching, anodising etc. to name a few

Adhesively bonded aluminium joints have wide spread
applications in aerospace, automotive and general engineering
sectors because of their high strength-to-weight ratio, excellent
corrosion resistance and improved manufacturability compared
to those made by traditional welding techniques [1–4]. The
durability of the adhesive bond strength and the long service life
under demanding conditions necessitates the pre-treatment of
the surface before adhesive bonding. Aluminium surfaces are
usually covered with a weakly bound naturally formed surface
oxide layer and adsorbed contamination, which needs to be
removed to establish a durable bond between the metal and the
adhesive. Various mechanical, chemical and electrochemical
surface pre-treatment methods have been reported for alumi-
nium substrates like liquid or vapour degreasing, abrading, grit-
n
Corresponding author. Tel.: þ 91 4712564298.
E-mail addresses: leenakarthi@yahoo.co.in (K. Leena),
athukannan@gmail.com (K.K. Athira), sbvssc@gmail.com (S. Bhuvaneswari),
surajvssc@gmail.com (S. Suraj), rao_vl@yahoo.co.in (V.L. Rao).
1
Present address: Four dimensional X-ray microscopy lab, Department of
Mechanical Engineering, IIT Bombay, Powai, Mumbai-400076, India
[5–12]. A full review on the surface pre-treatments for aluminium
alloys has been reported elsewhere [13]. Alkaline etching
removes the unstable aluminium oxide/hydroxide film and
cleans the stubborn oils and greases off the bonding surfaces.
Vapour degreasing consists of removing oils and other organic
contaminants from the roughened surface using suitable sol-
vents. Boiling water can act as a surface treating agent for alu-
minium alloy which results in durable adhesive strength with
epoxy adhesive [14]. A combination of different pre-treatment
techniques such as grit-blasting, acetone degreasing, alkali
etching and phosphoric acid anodising, provides a better adhe-
sive bonding property for aluminium alloys [15]. The most
exploited chemical pre-treatment for aluminium adherents is
based on chromic-sulphuric acid etching which generates a sui-
table oxide layer on the substrate surface and can produce strong
and durable adhesive bonds [16].
The surface pre-treatment method adopted for the adherent
would greatly influence the contact angle. An aluminium alloy
surface after alkaline etching, dipping in warm water followed by
treating with silane solution showed a decreased contact angle for
water and a polyurethane adhesive on the surface [17]. A higher

http://dx.doi.org/10.1016/j.ijadhadh.2016.07.012
0143-7496/& 2016 Elsevier Ltd. All rights reserved.
266 K. Leena et al. / International Journal of Adhesion & Adhesives 70 (2016) 265–270
surface roughness of the adherent favoured the spreading of the
adhesive drop on its surface. Studies conducted elsewhere have
shown that surface roughness and chemical heterogeneities
greatly influence the contact angle values of the adhesive formed
on the adherent surface [18–21].
One of the factors deciding the durability of an adhesive joint is
the extent of penetration of the adhesive into the pores of the
surface film formed after the pre-treatment [22]. The penetration
of the adhesive depends on many factors such as pore dimensions,
contact angle between the adhesive and the substrate, viscosity of
the adhesive and the viscosity–time characteristics at the tem-
perature of applications [23]. In the case of adhesively bonded
aluminium, there have been comparatively few studies on the
influence of surface roughness on joint strength. It has been
reported that a commonly used chromate pre-treatment improves
the lap shear strength of bonded joints with optimal joint strength
corresponding to a surface morphology consisting of etch pits of
1–5 mm in diameter [24]. Similar structures have been reported,
where the etched and anodised aluminium surfaces were scanned
using transmission electron microscopy (TEM) [25,26]. These
workers have attributed much of the increase in joint strength of
pre-treated aluminium to fine scale oxide structures.
The present study is focused on the effectiveness of various
surface pre-treatments for producing strong adhesive bonds on
aluminium interfaces which is evaluated using the single lap shear
test with an epoxy adhesive. The influence of surface energy,
contact angle, surface topography and surface roughness on the
experimental shear strength properties of aluminium substrates
was explored.
2. Materials and methods
2.1. Materials
Aluminium alloy, B51 SWP was used as the substrate. The
adhesive employed was an epoxy resin supplied by M/s. Hunts-
man India pvt. ltd., cured at 100 °C with o,o0 Bis(2-aminopropyl)
polypropylene glycol purchased from M/s. Sigma Aldrich, India.
BR127, purchased from M/s. Cytec Industries Inc.,USA was used for
priming the aluminium substrates. Diidomethane, 98% and water
(HPLC grade), used as the reference liquids for measuring the
surface energy of the aluminium substrates, was obtained from
M/s. Spectrochem, India. Trichloroethylene 99.9% from M/s. Nice,
India was used as the solvent. The FPL etch solution was prepared
as per the standard procedure given elsewhere [27].
2.2. Methods
2.2.1. Substrate preparation
All the substrate surfaces were initially abraded using P100
grade emery paper and any emery dust was removed with a clean
forced air supply. The substrate surfaces were subjected to three
different types of pre-treatment as follows.
2.2.1.1. Solvent degreasing (method a). Solvent degreasing was
conducted by wiping the surface using a lint free cotton cloth
soaked with trichloroethylene solvent followed by drying with a
hot air stream which did not exceed a temperature of 60 °C. This
surface was designated as Al-SD.
2.2.1.2. Method a followed by FPL etching (method b). This involved
immersion in an FPL etch solution for 15 min. at 60 °C, followed by
rinsing in tap water and drying with a hot air stream at a tem-
perature not exceeding 60 °C. The resulting surface was designated
as Al-SDFPL.
2.2.1.3. Method b followed by primer application (method c).
Aluminium substrates were primed immediately after method b.
Substrates were dipped in primer BR127, kept in a vertical position
for removal of excess primer at room temperature for 30 min. and
further cured at 120 °C for 30 min. in a hot air oven. This surface
was designated as Al-SDFPLP.
2.2.2. Substrate surface characterisation
The substrate surface was analysed for surface energy, contact
angle, surface topography, roughness and adhesive strength
properties. The contact angles of the reference liquids and the
dynamic contact angle of an epoxy adhesive on variously pre-
treated aluminium substrates were analysed using a sessile drop
technique using a video based optical contact angle measuring
equipment OCA20 (M/s. Data Physics, Germany). The surface
energy of the substrates, which is calculated as the sum of the
polar and dispersive components were measured by the Owens
Wendt Rabel Kaelble (OWRK) method [28,29]. The theoretical
work of adhesion of the epoxy adhesive on the variously
pre-treated substrates was determined using the Dupre-Young
equation. Single lap shear strength of the bonded joints was
determined according to ASTM D1002-72. The testing was carried
out with a universal testing machine (UTM) Instron Model 5569,
where, five samples were tested in each case. The surface topo-
graphy of the various pre-treated aluminium substrates was
measured using a 300R atomic force microscope (M/s. WILec,
Alpha, Germany) in a non-contact mode at a scanning speed of
1 μm/s. for an analysing area of 100 μ  100 μ. All the images had
256 data points with a scan rate of 1.0 line/s. Three individual scan
areas were considered and the roughness values were averaged to
calculate the surface roughness using WITec project plus software.
3. Results and discussion
The substrate surfaces after various pre-treatments were ana-
lysed for contact angle, surface energy, surface topography and
adhesive strength properties.
3.1. Surface energy
The contact angles made by the reference liquids water and
diiodomethane on an aluminium substrate surface after the three
pre-treatment techniques are reported in Table 1.
The variation of the dispersive and polar components of surface
free energy and the total surface energy of the various surfaces
studied are given in Fig. 1a–c respectively.
Fig. 1a indicates that even though the surface energy con-
tribution of the dispersive component is high in comparison to the
polar component, the variation is minimal for the different pre-
treated surfaces. Fig. 1b shows that the variation in the polar
contribution is more prominent in determining the total surface
energy. The contribution by the polar component is the highest for
the Al-SDFPL surface due to the freshly formed aluminium oxide
layer on the surface and lowest for the primed surface. Hence the
Table 1
Average contact angles in degrees shown by two reference liquids and the surface
roughness average of variously pre-treated aluminium substrates.
System Contact angle (°) Surface roughness Ra (nm)
H2O CH2I2
Al-SD 76 63 530
Al-SDFPL 32 56 620
Al-SDFPLP 93 54 390
 K. Leena et al. / International Journal of Adhesion & Adhesives 70 (2016) 265–270
Fig. 1. Variation of dispersive part (a), polar part (b) and the total surface energy (c)
of the pre-treated aluminium substrates.
Al-SDFPL substrate showed the highest total surface energy among
the various substrates as shown in Fig. 1c. This is because chromic
acid etching removes weakly bound oxide layer from the surface
267
and creates a fresh and strong oxide layer by the FPL treatment. It
has been reported that acid treatment generates a thin oxide layer
of the order of 10 nm on the aluminium surface [1,4]. The Al-SD
substrate showed a considerably lower surface energy (36 mN/m)
than the Al-SDFPL substrate (64 mN/m). This can be attributed to
solvent degreasing which removes oils and other organic con-
taminants from the substrate surface and does not contribute to
the removal of the weakly bound thin aluminium oxide layer. The
decreased surface energy of the AL-SDFPLP surface can be attrib-
uted to the lower surface energy of the epoxy based primer
coating on the surface as indicated by a higher contact angle (93°)
for the polar and lower contact angle (54°) for the non-polar
reference liquids.
3.2. Contact angle measurements of epoxy adhesive
The contact angle of the epoxy adhesive imaged 600 ms fol-
lowing application of a drop on each substrate surface is shown in
Fig. 2. The trend in the variation of contact angle values as a
function of time following application of the drop is depicted in
Fig. 3. All substrates exhibited the same trend in the variation of
contact angle with respect to time. Contact angle for the Al-SD
substrate showed an initial value of 84°, then stabilised at 65°,
whereas, Al-SDFPL substrate showed an initial contact angle of
72°, then stabilised at a lower value of 45°. The absorption of the
adhesive on a substrate depends on many factors such as the
surface energies of the adhesive and substrate, the geometry of the
pores, rheology of the adhesive and the time since application. For
the Al-SD substrate, even if the oils and organic contaminants are
removed, the weakly bound oxide layer hinders the spreading of
the adhesive. For Al-SDFPL substrate, the increased surface energy
and the uniform porosity after the chromic acid etching resulted in
more penetration of the adhesive into the surface pores resulting
in good wetting and a lower contact angle. Al-SDFPLP substrates,
even though they showed a lower surface energy, the epoxy
adhesive showed good wetting on its surface, giving an initial
contact angle of 68°, followed by stabilisation at 25°. This may be
attributed to the increased interaction of the epoxy /primer
interface thereby increasing the wetting of the resin on to the
surface.
3.3. Theoretical work of adhesion from contact angle measurement
The stabilised contact angles for each substrate were taken for
computing the work of adhesion. The surface energy of the liquid
epoxy resin used was determined as 40 mJ/m2 by the pendent
drop method using the contact angle goniometer. The plot for the
work of adhesion for each type of substrate is given in Fig. 4. The
lowest work of adhesion for Al-SD, which has undergone a non-
efficient surface preparation method, is attributed to the existence
of a weak boundary layer on the surface. As expected, the Al-SDFPL
showed a higher work of adhesion compared to Al-SD which is
evident due to the presence of the fresh and porous aluminium
oxide layer on the substrate after the pre-treatment. For Al-
SDFPLP, the good interfacial interaction of the epoxy primed sub-
strate and the epoxy adhesive played a greater role than the sur-
face energy of the substrate in improving the work of adhesion
which was earlier proven by achieving the lowest contact angle of
25° by the epoxy adhesive.
The trend obtained in the theoretical work of adhesion is fur-
ther substantiated experimentally by measuring the single lap
shear properties of the variously pre-treated aluminium substrates
using the epoxy adhesive system. The results are given in Fig. 5. A
positive correlation exists between the theoretical work of adhe-
sion and the experimentally measured lap shear strength prop-
erties for Al-SD and Al-SDFPL substrates. The AL-SD substrates
268 K. Leena et al. / International Journal of Adhesion & Adhesives 70 (2016) 265–270
Fig. 2. Stabilised contact angles of epoxy adhesive on variously pre-treated aluminium surfaces (a) Al-SD (b) Al-SDFPL and (c) Al-SDFPLP.
Fig. 3. Dynamic contact angle vs. drop age for various pre-treated aluminium substrates.
Fig. 4. Theoretical work of adhesion vs. various surface pre-treatments.
Fig. 5. Lap shear strength of various pre-treated aluminium substrates.
showed the lowest and the Al-SDFPL substrate showed the highest
shear strength properties. Even if Al-SDFPL substrate showed
lower theoretical work of adhesion than Al-SDFPLP, their practical
adhesive strength was comparable. This may be attributed to the
other contributing factors such as surface roughness of the
adherent, interfacial contact area, surface energy and chemical
composition of adhesive and adherent; nature of the adhesive etc.
in determining the practical adhesive strength.
3.4. Surface topography and roughness by AFM
One of the limitations encountered with surface studies was in
quantifying the surface roughness of adherents and correlation to
adhesion parameters. The recent development in AFM enables
both imaging and the quantification of surface roughness to sub-
nanometre resolution. In the present study, each of the pre-treated
aluminium substrates was subjected to AFM imaging to under-
stand the surface texture and surface roughness. The AFM images
 K. Leena et al. / International Journal of Adhesion & Adhesives 70 (2016) 265–270
Fig. 6. Surface topography by AFM of (a) Al-SD (b) Al-SDFPL and (c) Al-SDFPLP substrates.
of the pre-treated substrates are depicted in Fig. 6 and the mea-
sured surface roughness are given in Table 1.
The Al-SD substrate showed a compact, less random surface
with uniform peaks visually. Al-SDFPL showed a perfectly random
porous texture with predominant valleys or pits and has given a
roughness average, Ra, of 620 nm. This is attributed to the oxide
protrusions which serve the mechanical interlocking and very
good interfacial interaction with the epoxy. This has resulted in the
highest lap shear strength for aluminium substrates as discussed
in the previous section. Al-SDFPLP substrate showed a perfectly
random surface with predominant peaks but showed a lower
surface roughness average of 390 nm. This may be due to the
entrapment of the primer into the pits formed during the FPL
etching as shown in the AFM images. The study confirms that a
combination of high surface energy, high surface roughness and
good wettability of the adhesive altogether contributed for the
highest joint strength for the aluminium alloy substrates through
the FPL etching pre-treatments.
4. Conclusion
In this study, aluminium substrates were subjected to three
different surface pre-treatment techniques. The substrate surfaces
after various pre-treatments were analysed for contact angle,
surface energy, surface topography and adhesive strength prop-
erties. The aluminium substrate which had undergone only the
solvent degreasing pre-treatment technique showed a lower sur-
face energy than the FPL etched surface. It showed a comparatively
poor wetting of epoxy adhesive on its surface and lower surface
roughness than the FPL etched surface which resulted in the
lowest theoretical work of adhesion and practical adhesive
strength. The FPL etching of the substrate resulted in good wetting
by the epoxy adhesive, highest surface energy and surface
269
roughness thereby highest lap shear strength properties. The
primed aluminium substrate showed very good interfacial inter-
action with the epoxy adhesive resulting in comparable lap shear
strength properties to that of FPL etched surfaces.
Acknowledgement
The authors thank the authorities of Vikram Sarabhai Space Centre
for giving permission to publish the article. One of the authors,
K.K. Athira is thankful to the National Institute of Technology, Calicut,
Kerala, for permitting to conduct her academic project work on this
topic. Thanks are also due to the Analytical and Spectroscopy Division
of the Vikram Sarabhai Space Centre for analytical support.
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