I~UTTERWQRTH &t. J.

Adhesion and Adhesives 15 (1995) 87 90

I~E I N E M A N N Elsevier Science Limited
Printed in Great Britain
0143-7496/95/$10.00

Treatment of low energy surfaces for adhesive

bonding

D.M. Brewis*, I. Mathieson and M. Wolfensberger*

Institute of Surface Science and Technology, University of Technology,
Loughborough, Leicestershire LE11 3TU, UK

Surface pretreatment methods to enhance adhesion to polymers with low surface energies generally either
remove a region of low strength from the surface or introduce new surface functional groups. The
relative importance of these two mechanisms is examined in the present paper for various combinations
of pretreatment and polymer.

(Keywords: adhesive bonding; polymers; surface pretreatment)

INTRODUCTION transferred at low loads to an epoxide adhesive 1. Some

Organic molecules including polymers possess low
surface energies. The poor adhesion to some polymers
has often been ascribed to this low surface energy, but
an alternative reason has also been proposed, namely
the existence of weak boundary layers - i.e. a region of
low cohesive strength between the polymer and the
adhesive. Many pretreatments are available to enhance
the adhesion to polymers. These pretreatments range
from a solvent wipe for poly(vinyl chloride) (PVC), to
grit blasting for composites, and to flame treatment for
polyolefins. In the first case the pretreatment removes a
region of low strength from the surfaces. In other cases
a pretreatment may be effective by introducing new
functional groups into a surface or by a combination
of the two mechanisms.
In the present paper, the relative importance of these
two mechanisms is examined for various combinations
of pretreatment and polymer. These combinations are
the sodium complex and plasma treatments of fluori-
nated polymers, the reversible bromination of polyethyl-
enes, and the treatment of poly(ether ether ketone)
(PEEK) with a flame and also with chromic acid. The
epoxide adhesive used in all experiments was Araldite
AV100 with HVI00 hardener.
improvements in adhesion to chemically unmodified
P T F E have been achieved. In multiple bonding experi-
ments where an epoxide was bonded many times to the
same piece of PTFE, a 2.2 fold increase in bond
strength occurred2; this may have been due in part to
an increase in roughness. Plasma treatment (Table 1)
resulted in a fourfold increase in joint strength without
significant change in surface chemistry as determined
by X-ray photoelectron spectroscopy (XPS) 3.
To achieve high adhesion levels with PTFE, it may
be that substantial chemical modification is required as
is achieved with the commercial sodium complex
treatment Tetra-Etch (Table 2).
Cls
Fls
C KLL
g F 2s
KLL O ls I I
,-n

FLUOROPOLYMERS

The existence of a weak boundary layer has been I I I I I I I I '2 o o

1000 800 600 400
demonstrated in the case of polytetrafluoroethylene
4 Bindingenergy (eV)
(PTFE). Figure 1 shows that fluorinated material was
Figure I XPS broad scan of the surface of an epoxide adhesive
* To whom correspondence should be addressed which had been cured in contact with PTFE. The PTFE was
~Visiting scientist from the Swiss Federal Laboratories for Materials detached from the epoxide at a low failure load but transfer of fluori-
Testing and Research (EMPA), Switzerland nated material has clearly taken place (ref. 1, with permission)

INT. J. ADHESION AND ADHESIVES Volume 15 Number 2 1995 87

Treatment of low energy surfaces: D.M. Brewis et al.

Table I Surfaceanalysis and bond strengths of poly(vinyl fluoride) (PVF) and PTFE after plasma treatments

XPS (atom%)
Polymer Plasma C O F Failure load (N)

PVF None 70.4 0.8 28.8 360

Ar, I rain 71.3 11.0 17.7 4060
Ar, 30min 78.0 11.9 10.1 4540
02, I rain 66.3 12.4 21.3 3420
Air, I rain 66.8 8.0 25.2 3080
N2, I rain 66.5 5.8 27.7 2720
PTFE None 34.6 65.4 420
Ar, I min 42.1 4.5 53.4 1340
Ar, 5 rain 33.1 1.6 65.3 1400
Ar, 30 min 33.5 0.9 65.6 1860
Ar, 60 min 32.8 0.2 67.0 1660
02, I rain 34.4 65.6 1080
O~, 10min 33.6 0.2 66.2 1440
02, 30min 34.0 0.5 65.5 640

Table 2 Effect of Tetra-Etch treatment on PTFE, PVF and poly(vinylidenefluoride) (PVdF)

Polymer, XPS (atom%)

treatment time Colour C F O Failure load (N)

PTFE, none white 38.4 61.6 0 420

PTFE, 10 s brown 87.6 0.8 I 1.6 4280
PTFE, 1 rain black 82.2 0.9 16.9 4260
PVF, none colourless 70.4 28.8 0.8 360
PVF, 10 s colourless 72.4 26.7 0.9 8O0
PVF, 1rain colourless 75.4 23.0 1.6 2080
PVF, 60 min colourless 87.3 11.4 1.3 3020
(i
PVdF, none colourless 51.4 47.9 0.7
PVdF, 1min faint brown 77.4 12.9 9.7 ¢1

PVdF, 60 min faint brown 79.5 9.2 11.3

"Not measured

There is an interesting contrast in the T e t r a - E t c h
t r e a t m e n t s of P T F E a n d poly(vinyl fluoride) (PVF).
The chemical modifications at a given t r e a t m e n t time
are m u c h more p r o n o u n c e d with P T F E . In the case of
PVF, large increases in j o i n t strength are o b t a i n e d
w i t h o u t i n t r o d u c i n g a s u b s t a n t i a l q u a n t i t y of oxygen-
c o n t a i n i n g f u n c t i o n a l groups. This indicates that
i m p r o v e m e n t in adhesion is m a i n l y due to the elimina-
tion of a potential weak b o u n d a r y layer. This is
supported by the fact that a n o t h e r batch of P V F gave
good adhesion to the same epoxide adhesive w i t h o u t a
p r e t r e a t m e n t 4, A l t h o u g h the surface energies of P V F
a n d poly(vinylidene fluoride) (PVdF) are similar to
that of polyethylene, the former two polymers are
polar ~ a n d therefore relatively strong interactions can
be achieved to an epoxide. In some cases chemical
b o n d i n g m a y occur between the f l u o r o p o l y m e r a n d the
epoxide adhesive 6,
substantial changes occur to the surface chemistry v 9. It
has been argued that good adhesion can be o b t a i n e d to
chemically u n m o d i f i e d polyolefins l°'tl but there is no
clear evidence to s u p p o r t this ~2. However, there is good
evidence to show that the p o o r adhesion o b t a i n e d with
u n t r e a t e d polyolefins is due to a lack of f u n c t i o n a l
groups. F o r example, work by Chew et al. 13 showed
that large increases in j o i n t strength were o b t a i n e d
when low density polyethylene ( L D P E ) a n d high
density polyethylene ( H D P E ) were b r o m i n a t e d (Figure
2). However, the j o i n t strengths returned to very low
B r 2 / hv

--CH2--CH2-- CH2--CHBr--
POLYOLEFINS

C o r o n a t r e a t m e n t is the most c o m m o n l y used pretreat-

m e n t for polyolefin films whereas flame t r e a t m e n t is
usually used for thicker sections of polyolefin such as
bottles. C h r o m i c acid is sometimes used where the TBTH
p o l y m e r has a complex shape. In all these cases Figure 2 The reversible bromination of polyethylene13

88 INT. J. ADHESION AND ADHESIVES Volume 15 Number 2 1995

 Treatment of low energy surfaces: D.M. Brewis et al.

Table 3 Effect of bromination and subsequent reduction of Table 5 Joint strengths obtained with untreated and treated PEEK
polyethylene on joint strength
Failure load (kN)"
Joint strength XPS data
Polymer (MPa) Br:C (atom%) Treatment Batch 1 Batch 2

Untreated LDPE 1.4 0 None 2.8 0.7

Brominated LDPE (A) 12.7 11
Reduction of (A) 1.8 0 Chromic acid" (1 min, 60C)
Untreated HDPE 0.7 0 Chromic acid (1 min, 33°C)
Brominated HDPE (B) 11.5 5.9
Reduction of (B) 0.8 0 ~Film of PEEK bonded with an epoxide to two mild steel strips
levels when the brominated polyethylenes were reduced
back to polyethylene with tributyltinhydride (TBTH) in
m e t h y l t e t r a h y d r o f u r a n as shown in Table 3.
Further evidence to support the view that p o o r
adhesion with polyolefins is due to a lack o f functional-
ity rather than weak b o u n d a r y layers is given by the
work o f Brewis j4 in which he deliberately added a layer
o f low cohesive strength ( h y d r o c a r b o n grease) to a
chromic acid treated H D P E . The results are given in
Table 4. Addition o f the h y d r o c a r b o n grease caused
some reduction in joint strength but the value remained
much higher than that o f the untreated polymer. This
means that the grease layer, which was about 1 #m
thick, was absorbed by the epoxide adhesive. The
implication o f this work is that even if there is a region
of low cohesive strength on a polymer surface, due to
low molecular weight polymer or additives, it need not
necessarily behave as a weak b o u n d a r y layer. Whether
the layer is absorbed will depend on various factors
including the thickness o f the layer, the compatibility
between the layer and the adhesive, the temperature
and the time the adhesive takes to harden.
POLY(ETHER ETHER KETONE)
P E E K possesses a reasonable degree o f functionality,
i.e.
O
-o-@-o-©-c- II
and p o o r adhesion to untreated P E E K would not be
expected from its structure. In a recent study ~5 g o o d
adhesion was obtained to one batch o f P E E K but p o o r
adhesion was obtained to another (Table 5).
Flame treatment caused a substantial improvement
in adhesion to batch 1. XPS indicated no significant
Table 4 Effect of added layer of hydrocarbon grease to joint
strength with chromic acid treated HDPE
Lap shear
Treatment strength (MPa)
None 1.8
Chromic acid (C) 17.6
As (C) but layer of hydrocarbon added 12.7
Flamet' 4.9 0.9
4.0
Chromic acid (5 min, 35"C) 3.2
3.1
(60mm long × 20mm wide) so the overlap area is 20mm × 10mm
hFlame treatment was for 0.012 s
'The chromic acid comprised potassium dichromate, water and
concentrated sulfuric acid in the ratio 7:12:150 by weight
differences between the two untreated materials. The
likely cause o f the p o o r adhesion with batch 2 is an
inadequate degree o f polymerization. Flame treatment
m a y chemically modify the surface o f batch 2 but if a
region o f low cohesive strength which cannot be
absorbed by the adhesive remains, then p o o r adhesion
will result. The success o f the chromic acid treatment is
presumably due to dissolution o f the relatively low
molecular weight material on the surface o f the P E E K
(batch 2).
CONCLUSIONS
l) To obtain high adhesion levels to fully fluorinated
polymers such as P T F E and to polyolefins, it is
p r o b a b l y necessary to significantly modify their
surface chemistry.
2) Most other polymers contain sufficient functionality
to achieve at least reasonable joint strengths. If
p o o r adhesion is obtained with these polymers, it is
probably due to a weak b o u n d a r y layer.
3) With partially fluorinated polymers such as P V F
and P V d F g o o d adhesion can be achieved without a
pretreatment. However, some batches o f these
polymers may have regions o f low cohesive strength
on their surfaces and thus require a pretreatment.
4) There is sufficient functionality in untreated P E E K
to achieve g o o d adhesion but regions o f low
cohesive strength on the surface m a y lead to p o o r
adhesion with a given batch o f polymer.
REFERENCES
1 Briggs,D. in 'Industrial Adhesion Problems' (Eds D.M, Brewis
and D. Briggs), Orbital Press, Oxford, 1985, p. 15
2 Brewis, D.M., Mathieson, I., Sutherland, 1. and Cayless, R.A.J.
Adhes. 1993, 41, 113
3 Mathieson, I., Brewis, D.M., Sutherland, I., Cayless, R.A.J.
Adhes. 1994, 46, 49
4 Brewis, D.M. Prog. Rubber Plast. Technol. 1985, 1(4), 1
5 Rance, D.G. in 'Industrial Adhesion Problems' (Eds D.M.
Brewis and D. Briggs), Orbital Press, Oxford, 1985, p. 121
6 Schonhorn, H. and Luongo, J.P.J. Adhes. Sci. Technol. 1989,
3(4), 2277
7 Briggs,D. and Kendall, C.R. Int. J. Adhes. Adhes. 1982, 2, 13
8 Briggs D., Brewis, D.M. and Konieczko, M.B.J. Mater. Sci
1979, 14, 1344

INT. J. ADHESION AND ADHESIVES Volume 15 Number 2 1995 89

Treatment of low energy surfaces: D.M. Brewis et al.

9 Briggs D., Brewis, D.M. and Konieczko, M.B.J. Mater. Sci 12 Brewis, D.M. Int. J. Adhes. Adhes. 1993, 13(4), 251
1976, 11, 1270 13 Chew, A., Dahm, R.H., Brewis, D.M., Briggs, D. and Rance,
10 Schonhorn, H. and Hansen, R.H.J. Appl. Polym. Sci. 1967, 11, D.G.J. Colloid Interf. Sci, 1986, 110(1), 88
1461 14 Brewis, D.M.J. Mater. Sci. 1968, 3(3), 262
11 Blais, P., Carlsson, DJ., Csullog, G.W. and Wiles, D . M . J . 15 Brewis, D.M., Mathieson, I. and Wolfensberger, M. unpub-
Colloid InterJ~ Sci. 1974, 47, 610 lished work

90 INT. J. ADHESION AND ADHESIVES Volume 15 Number 2 1995