International Journal of Adhesion and Adhesives 95 (2019) 102433

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International Journal of Adhesion and Adhesives

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

Polybenzimidazole adhesive bonded aluminum-2024 joints for structural T

applications
Muhammad Faisal Shahzada,∗, M.P. Mughala, H.M.S. Iqbalb, N.A. Muftia, M.Q. Saleema
a
Department of Industrial & Manufacturing Engineering, University of Engineering & Technology, Lahore, Pakistan
b
Department of Mechanical Engineering, Superior University, Raiwind Road, Lahore, Pakistan

ARTICLE INFO ABSTRACT

Keywords: In the present research, efforts are made to optimize the curing process and bonded joint strength of aluminum
High temperature adhesive 2024 alloy (Al 2024-T3) using polybenzimidazole (PBI) adhesive. Substrate surfaces were prepared using P120
Aluminum alloys and P1000 sand papers followed by cleaning with ethanol. Substrate surfaces were also prepared using tri-
Surface treatment Sodium phosphate (TSP) and the Forest Product Laboratory (FPL) method. Contact angle measurements of
Contact angle
untreated surfaces revealed that ethanol cleaned Al 2024-T3 strips exhibited a water contact angle of 86°. A
Lap shear
Microscopy
significant decrease in the water contact angle for Al 2024-T3 was noticed with P1000 sanding followed by TSP
treatment. The water contact angle of Al 2024-T3 was reduced from 86° to 52° using a combined surface
treatment of P1000 sand paper and TSP solution. Lap shear tests were performed to evaluate the single lap shear
strength of PBI bonded Al 2024-T3 joints. A maximum lap shear strength of 11.9 MPa was achieved for samples
which had received a combined surface treatment of P1000 sand paper and TSP solution. A lap shear strength of
12.1 MPa was achieved using the FPL treatment method. This lap shear strength is almost similar as attained
with TSP treated bonded joints. Therefore, the current work also proved TSP as an effective alternative to the
hazardous chromate based FPL method for the surface pre-treatment of Al 2024-T3. Fractured surfaces of ad-
hesive bonded joints revealed both adhesive and cohesive failure.

1. Introduction
Adhesive bonding offers many advantages for structural assemblies
over conventional joining techniques [1]. Poor weldability, dissimilar
nature of joining materials and undesired alteration in properties of the
metals due to the heat produced during the welding of structural
components are of no limitations for adhesive bonding [2]. It also
provides advantages of uniform stress distribution compared to me-
chanical screwing and fastening techniques [3]. Furthermore, the pro-
blem of fatigue in mechanical joining elements such as rivets, screws
and fasteners and their lower strength to weight ratios are successfully
resolved by adhesive bonding technology [4].
For high temperature applications, structural adhesives meet the
strength requirements in the temperature range between 200 °C and
250 °C [5,6]. Application of structural adhesives is mainly dependent on
the glass transition temperature (Tg) of these adhesives [7]. Higher Tg
provides the desired properties of the adhesives to withstand higher
service temperatures [8]. But, at the same time, higher Tg increases
processability requirements of polymeric adhesives, limiting their use
due to higher costs and manufacturing difficulties. PBI is a high
performance polymer known for its highest Tg (425 °C) and tensile
strength (160 MPa). Due to its highly amorphous nature, PBI has no
melting point and only softens above 425 °C. Due to the very high Tg,
the processing of PBI requires high temperature and high pressure au-
toclave processing, limiting its applications due to process ability
challenge [9–15]. To overcome the challenge of processing, PBI is now
commercially available in solution form. In this form, PBI has been
investigated for high temperature fuel cell applications due to its high
thermal stability [16].
Recently, research has been conducted using a PBI solution to
evaluate the application of PBI as a fire retardant coating material [17].
In other work, PBI has been explored as an adhesive for composite
substrates. A maximum lap shear strength of 30 MPa was achieved for
carbon/epoxy composite bonded joints using PBI adhesive. However,
due to the lower Tg of the composite substrate, curing of bonded joints
was limited to 125 °C [18]. Therefore, the bonding potential of PBI
could not be fully explored in this earlier study. Further investigation is
required to evaluate the performance of PBI adhesive while curing at a
higher temperature than that employed in the previous research.
In the context of the above mentioned facts, the main objective of

∗
Corresponding author.
E-mail address: faisaltaj636@gmail.com (M.F. Shahzad).

https://doi.org/10.1016/j.ijadhadh.2019.102433
Received 26 March 2019; Accepted 24 August 2019
Available online 27 August 2019
0143-7496/ © 2019 Elsevier Ltd. All rights reserved.
M.F. Shahzad, et al. International Journal of Adhesion and Adhesives 95 (2019) 102433

the current work was to evaluate the bonding strength of PBI adhesive
while curing it at higher temperature than the curing temperature used
previously. Al 2024-T3 was selected as the substrate material for pre-
paring PBI adhesive bonded joints. Al 2024-T3 possesses a higher
melting temperature (425 °C) than PBI with similar coefficient of
thermal expansions. However, poor weldability is a major issue for Al
2024-T3 joint assemblies, limiting its widespread structural application
[19–21]. Therefore, another objective of this work was to evaluate the
performance of Al 2024-T3 bonded joints using PBI adhesive.

2. Experimental methods

Fig. 1. Contact angle measurement of different samples using KRUSS DSA 30.
2.1. Materials

98% industrial grade tri-sodium phosphate (TSP), for mild etching
of Al 2024-T3, was provided by Qingzhou Zhongyuan Chemical
Industry Co., Ltd. (China) Al 2024-T3 sheet of 3 mm thickness was
supplied by Wuxi Campat Aluminium Industry Co. Ltd (China) for use
as substrate. 99% pure ethanol was provided by Sigma – Aldrich
(Merck) for the cleaning and degreasing of Al 2024-T3. Silicon carbide
(SiC) P1000 and P120 sandpapers were supplied by Kwang Myung
Abrasive Co.(KMCA) Korea. 26% concentrated solution of PBI in N,N-
dimethylacetamide (DMAc) was supplied by PBI Performance Products,
Inc., US for use as adhesive. 99% pure DMAc was supplied by
DAEJUNG, Korea to further dilute the solution of PBI. 95% pure sul-
phuric acid (H2SO4), 99% pure sodium dichromate dehydrate
(Na2Cr2O7 · 2H2O) and distilled water were supplied by DAEJUNG,
Korea to prepare the etching solution as per the Forest Products
Laboratory (FPL) method.
2.4. Contact angle measurement
Water contact angles of both untreated and treated surfaces were
measured using the KRUSS DSA 30, Drop Shape Analyzer shown in
Fig. 1. Three readings for all surfaces were taken and the average was
calculated.
2.5. Microscopic imaging
The surface morphology of untreated and treated samples was
analyzed with the help of the STM 6 optical microscope.
2.6. Sample preparation for lap shear testing

Samples with different surface treatment methods were prepared for

2.2. Surface preparation preparation of PBI adhesive bonded joints. All samples were degreased
using ethanol followed by one of the proposed surface treatments as
2.2.1. Pre-treatment using manual sanding shown in Fig. 2.
Al 2024-T3 sheet was cut to size as per ASTM D-1002 guidelines.
Samples were first cleaned and degreased with ethanol followed by
sanding with P120 and P1000 sand papers. All sanded strips were re- 2.7. Bonded joint preparation using 26% PBI solution
cleaned with ethanol for removal of impurities left as a result of
sanding. Reference samples were only cleaned and degreased with Bonded joints of Al 2024-T3 for single lap shear testing were pre-
ethanol for comparison purpose. pared using 26% concentrated PBI adhesive. Mechanical pressure of
0.05 MPa was applied on the joints using metallic paper clips. Joint
2.2.2. Chemical pre-treatment methods assemblies were then placed in an oven and curing was done using the
Aluminum has been known to give better bonding results with the following thermal cycle: 45 min at 80 °C; 45 min at 120 °C; 15 min each
FPL treatment method [22]. But, due to the hazardous nature of the at 150 °C, 200 °C and 250 °C.
chromate content, an alternative chemical treatment method is re-
quired which may produce the same treatment effect as attained by the
2.8. Sample preparation using 17% PBI solution
FPL method. For this purpose, a TSP solution was used as an alternative
chemical treatment method for comparing the performance of PBI
The as received PBI solution was a 26% concentrated highly viscous
bonded Al 2024-T3.
solution in DMAc solvent. It is reported in the literature that a decrease
Sanded samples were treated with a 5% (w/w) solution of TSP at
in solution viscosity enhances the wettability of substrates and hence
80 °C for 10 min, followed by a triple rinse in warm distilled water for
the adhesion strength of bonded joints [23]. Therefore, a 17% con-
10 min. The samples were re-cleaned with a neat cloth and placed in an
centrated PBI solution was prepared using DMAc in order to enhance
oven for drying at 80 °C for 15 min.
the wettability of Al 2024-T3 and to study the effect of viscosity on
The etching solution employed for the FPL method was prepared by
bonded joint strength. Bonded joints of Al 2024-T3 for single lap shear
mixing 10 parts by weight H2SO4, 1 part by weight Na2Cr2O7 · 2H2O
testing were prepared and joint assemblies were then placed in an oven
and 30 parts by weight of distilled water. Sanded samples were then
for curing at the following thermal cycle: 60 min at 80 °C; 45 min at
treated with this solution for 25 min followed by washing with warm
120 °C; 15 min each at 150 °C, 200 °C and 250 °C.
distilled water. These samples were further dried in an oven at 80 °C for
15 min.
2.9. Lap shear testing
2.3. Surface roughness measurement
Lap shear testing of bonded joints was performed in accordance
The roughness of untreated and treated surfaces was measured with the ASTM D - 1002 standard. The tests were conducted at a test
using a Taylor Hobson surface roughness meter. Five readings for all speed of 1.25 mm/min using a TIRA 2810 machine equipped with a
surfaces were taken and the average was calculated. 10 kN load cell.

2
M.F. Shahzad, et al.
Fig. 2. Schematic of surface treatments used for the preparation of single lap shear PBI bonded Al-2024-T3 joints.
3. Results and discussion
3.1. Surface roughness and contact angle measurement
Surface roughness and contact angle measurements of untreated
and treated surfaces were carried out and the results are shown in
Fig. 3.
Fig. 3 shows that untreated samples degreased with ethanol de-
monstrated an average surface roughness of 1.8 μm and a contact angle
of 86°. P120 sanded samples depicted an increase in surface roughness
from 1.8 μm to 2.9 μm. The contact angle of these samples also in-
creased from 86° to 92°. The increase in contact angle is more likely due
to the development of air pockets in the regions of deeper valleys
generated by P120 sanding. On the other hand, a decrease in surface
roughness and contact angle was observed for the samples treated with
P1000 sand papers. The surface roughness of P1000 treated samples
decreased from 2.9 μm to 1.2 μm and contact angle decreased from 92°
to 83°. A significant decrease in contact angle was noticed for samples
treated with TSP in comparison with simply ethanol cleaned samples.
The contact angle of TSP treated samples decreased from 86° to 64°
with a reduction of overall surface roughness from 1.8 μm to 1 μm
confirming a mildly etching behavior of TSP. The most significant effect
of surface treatment was observed for the samples sanded with P1000
Fig. 3. Effect of surface treatments on surface roughness and contact angle.
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International Journal of Adhesion and Adhesives 95 (2019) 102433
paper followed by chemical treatment using TSP solution. These sam-
ples depicted a decrease in contact angle from 86° to 52° and a decrease
in surface roughness from 2.9 μm to 0.7 μm, exhibiting best results in
the current work.
3.2. Microscopic imaging
The surface morphology of untreated and treated samples was
analyzed using optical microscopy. Microscopic images of surfaces with
different treatments are shown in Fig. 4.
Fig. 4(a) shows the surface morphology of untreated Al 2024-T3;
whereas, effects of the sanding and TSP treatment of Al2024-T3 are
shown in Fig. 4(b)–4(e).
Fig. 4(a) shows striation marks on the surface that reflects surface
imperfections such as pitting and scratch marks. For better adhesion
properties, a uniform surface with porous morphology is preferred [24].
Therefore, different surface treatments were performed in order to at-
tain the desired surface morphology. The striation pattern was altered
for the samples treated with P120 sand paper alone and in combination
with TSP treatment as shown in Fig. 4(b) and (d). The surface mor-
phology of the samples treated with P1000 sand paper alone and in
combination with TSP solution is shown in Fig. 4(c) and (e). The
samples 4(c) and 4(e) revealed a more uniform striation pattern due to
M.F. Shahzad, et al.
Fig. 4. Microscopic Imaging of Al 2024 substrate (a) untreated (b) P120 sanded and ethanol cleaned (c) P1000 sanded and ethanol cleaned (d) P120 sanded and TSP
treated (e) P1000 sanded and TSP treated.
fine sanding and mildly etching treatment of TSP. These striation pat-
terns are similar as described by other researchers in their research
work [25,26]. The combination of sanding with P1000 along with TSP
treatment has effectively changed the striation pattern and provided
more intimate contact between PBI and Al 2024-T3 surfaces. On the
other hand, deeper grooves as imparted by P120 sanding, in compar-
ison with P1000, may trap water and other contaminants. These
grooves are more likely to behave as pointed sharp edges, giving rise to
stresses on the PBI adhesive during tensile loading at the joint interface.
This may lead to brittle failure due to enhanced crazing phenomenon in
polymeric adhesive. The cracks generated during crazing of the ad-
hesive grow quickly followed by rapid rupture which results in a lower
lap shear strengths as observed by other researchers [27].
3.3. Lap shear test results
Lap shear testing of bonded joints, prepared with different surface
treatment methods, was performed to evaluate the strength of PBI ad-
hesive and the results are shown in Fig. 5.
Fig. 5. Lap shear strength of PBI bonded Al 2024 single lap joints.
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International Journal of Adhesion and Adhesives 95 (2019) 102433
Fig. 5 shows that untreated samples degreased with ethanol de-
picted a lap shear strength of 3.5 MPa. An increase in lap shear strength
was noticed for samples sanded with P1000 paper. These samples ex-
hibited a lap shear strength of 5.5 MPa which was further increased to
7 MPa by sanding the samples with P120. Further improvement in lap
shear strength of the bonded joints was observed for the un-sanded TSP
treated samples. Maximum lap shear strength was noticed for samples
treated with P1000 followed by TSP treatment. P1000 sanded and TSP
treated samples have demonstrated the lowest contact angle with finest
surface roughness among all treatments and ensured an intimate con-
tact between PBI and Al2024-T3 substrate, yielding better results for
lap shear strength.
3.3.1. Effect of adhesive viscosity on lap shear strength
In the present work, the effect of adhesive viscosity on the lap shear
strength of bonded joints was also studied. Fig. 6 shows the lap shear
strength of bonded joints prepared using 17% and 26% concentrated
PBI adhesive. It can be seen that the samples prepared with 26% con-
centrated solution exhibited better strength values irrespective of the
M.F. Shahzad, et al.
Fig. 6. Effect of adhesive viscosity on lap shear strength of bonded joints with different surface treatments.
higher viscosity due to the higher PBI concentration. It shows that the
higher viscosity of the adhesive helps to retain more adhesive in the
overlap area by reducing the flow of adhesive under pressure and
temperature. The retention of more adhesive in the bonded area re-
sulted in better lap shear strength in the current study. However, the
surfaces treated with P120 paper depicted a higher lap strength with
17% concentrated adhesive solution as compared to the lap shear
strength obtained with 26% PBI concentration. This behavior can be
attributed to the fact that increased surface roughness and decreased
viscosity due to lower PBI concentration resulted in better PBI retention
between the deeper valleys of the P120 sanded substrate, which was
accompanied with better mechanical locking phenomenon. However,
an optimum bonding condition resulting in a maximum lap shear
strength, was not achieved in this case.
3.4. Comparison of lap shear strength with TSP and FPL treatment
Lap shear strength of PBI adhesive bonded joints treated with TSP
and FPL method was also compared. Results in Fig. 7 show that the
samples treated with TSP solution depicted a lap shear strength of
11.9 MPa, whereas samples treated with the FPL method demonstrated
a lap shear strength of 12.1 MPa. These results suggest that the TSP
method can be used as an effective alternate for the chromate free
surface treatment of Al 2024-T3.
Fig. 7. Comparison of lap shear strength of PBI adhesive bonded joints using
FPL and TSP treatment method.
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International Journal of Adhesion and Adhesives 95 (2019) 102433
3.5. Failure mode
Failure modes of PBI adhesive bonded joints formed after different
surface treatments were studied and the results are presented in Fig. 8.
Fig. 8 shows that bonded joints exhibited different failure modes under
different surface treatment conditions. For untreated samples degreased
with ethanol and samples treated with P1000 sand paper, bonded joints
revealed an adhesive failure as shown in Fig. 8(a) and (b). Fractured
surfaces of bonded joints prepared with P120 sanded samples are
shown in Fig. 8(c). These samples exhibited a mix mode failure which is
likely due to the presence of air pockets resulting in more adhesive and
better bonding properties. Fractured surfaces of the samples treated
with P120 and P1000 sanded in combination with the TSP solution are
shown in Fig. 8(d) and (e). Samples treated with P1000 sanded in
combination with TSP solution depicted a mixed mode failure with
cohesive failure as the dominant failure mode. This indicates that a
more uniform porous surface morphology resulted in better wetting
properties and higher bonded joint strength.
4. Conclusions
In the present work, PBI was used as a structural adhesive for
joining Al 2024-T3 substrates using various surface treatments. The
work has shown a strong dependence of PBI bonded joint strength on
surface treatment method and PBI concentration. It was observed that
the 26% concentrated PBI adhesive exhibited better strength than the
17% concentrated PBI. It was also observed that an increase in viscosity
cannot be considered as the only parameter affecting the joint strength.
In fact, there exists an optimal combination of viscosity, pressure and
temperature that determines the maximum bonded joint strength
keeping in view the nature of the substrate and adhesive. A substantial
increase in lap shear strength was noticed for the samples treated with
TSP solution. An increase of about 240% in lap shear strength was
observed in comparison to the strength of untreated samples. Fracture
studies of failed joints demonstrated that a change in striation pattern
played an important role in achieving a better surface for bonding. A
uniform porous surface morphology ensures a better surface for adhe-
sion and hence yields a higher bond strength. This study further re-
vealed that the maximum lap shear strength achieved with TSP treated
surfaces was comparable with the strength achieved using the well
known FPL method. Therefore, TSP can be considered as an effective
alternative to the hazardous chromate based FPL method for treatment
M.F. Shahzad, et al.
Fig. 8. (a) Untreated (b) P120 sanded (c) P1000 sanded (d) P120 sanded and TSP treated (e) P1000 sanded and TSP treated.
of Al 2024. Outcomes of this research work are quiet encouraging and
will help the scientific community to understand and conduct further
research in the light of these results.
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