The metal/polymer interphase in

adhesive joints
J. Cognard

(Asulab SA, Switzerland)

Published experimental studies are reviewed to verify the validity of the assumption
that the columnar, cellular structure observed at certain polymer/metal interfaces can
be extended to apply to adhesive-bonded joints. It is shown that such a structure
would be consistent with the observed properties of thin joints.

Key words: adhesive-bondedjoints; interphase; structure; epoxy

Recent theories in adhesion science state that a three-
dimensional interphase, which exists between the
substrate and bulk adhesive in an adhesive-bonded
joint, governs the mechanical resistance and durability
of the joint I-3. Although experimental evidence of the
existence of the interphase and descriptions of its
structure are scarce, there are some experimental
results which allow insight into the structure of the
interfacial region. However, these results have been
obtained using a variety of experimental methods and
joint designs, and thus are rather like the elements of a
puzzle where some pieces are missing. Never the less
we are now able to draw a new picture of the metal/
polymer interface, although this cannot be a definite
representation.
This paper elucidates the structure of the polymer/
metal interphase by summarizing significant results in
the literature. Most of these were obtained either with
epoxy/metal or polyethylene/metal interfaces.
Aluminium and gold are commonly used as the
substrate in the adhesive bond, but zinc and copper
have also been considered. There is a risk in
generalization, but it may be assumed that although
the interphase may change quantitatively from one
polymer or substrate to another, the qualitative features
will be the same.
Nodular structure of the superficial layer of a
moulded epoxy resin
Cuthrell 4 showed by penetrometry and microscopic
observations that the superficial layer of an epoxy resin
moulded either in metal or polytetrafluoroethylene
(PTFE) consists of hard, spherical nodules separated by
channels of resin-like material. The size of the nodules
varies from 20 to 9 0 p m depending upon the
polymerization temperature of the resin and the
material comprising the mould. Large floccules are
obtained at low cure temperature and small ones at
high temperature. At a given temperature, large
floccules are formed in PTFE moulds and smaller ones
in metallic moulds. The nodular structure extends as
far as 100pro inside the sample, as shown
schematically in Fig. 1. Furthermore, Cuthrell was able
to show by electro-osmosis that the resin-like channels
were negatively charged. This structure was observed
for various epoxy resins cured either with amines or
acid anhydrides.
It will be shown that a similar structure, although
with different dimensions, forms within adhesive joints.
Cellular structure of the gold/epoxy interface
The sensitivity of adhesive joints toward stresses and
humidity is a puzzling problem that cannot be
explained from a knowledge of the bulk properties of
the adhesive and limits computer calculations of the
resistance of adhesive joints. M o d e m adhesives, once
2 0 - 9 0 pm
\
-'~;~. .:~; ~.
,"'.":~:,~'~ I 0 0 prn
-'..',.3
I 1
Fig. 1 Superficial structure of epoxy resin according to Cutl~rell 4

0143-7496/91/020114-03 © 1991 Butterworth-HeinemannLtd

114 INT.J.ADHESIONANDADHESIVESVOL.11 NO. 2 APRIL1991
 20pro
/

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Fig. 3 Schematic representation of the gold/epoxy interphase

Fig. 2 Ultrasonic microscopy of the gold/epoxy interface. Magnification

300x. Photograph taken by S. Sattish (EPFL)

polymerized, sustain stresses and are almost insensitive

to water. Under humid conditions, debonding is always
interfacial or near the interface 5. This suggests that the
interface is involved, but how, or what to do about it.
remains unknown. Silylation improves interfacial
properties, but why?
It was suspected that Cuthrell's results could be
related to the interphase structure. In an attempt to
gain some evidence supporting this assumption, and
Fig. 4 Scanning electron micrograph showing that the aluminium/epoxy
knowing the capabilities of ultrasonic microscopy to interphase has a columnar structure in the epoxy resin (KOtfing 11 with
observe materials through another one, ultrasonic permission)
microscopy was used to examine the gold/epoxy
interface". The interracial cellular structure was clearly
observed for a classical, amine-cured epoxy as well as a energy distribution of secondary emitted electrons. His
rubber-modified one (Fig. 2). Thus it appears that results show that there exists a distribution of negative
Cuthrell's observation of a nodular superficial structure charges in the first 10pm of the interfacial layer
is also true of the solid/epoxy interface (Fig. 3). If the (Fig. 5) that is attributed to electrons injected from the
cellular walls are actually charged and responsible for metal into the polymeric layer. This charge
the adhesion of the polymer (which remains to be distribution is related to the energy of adherence of
proven), then the influence of water on the interfacial polyethylene over aluminium 13.
properties can be understood as follows. The polar
interactions that are supposed to exist between the Ions in the interphase
adhesive and the substrate 7 can be identified as those In the course of a study 8 of the electrical conduction
arising from the electrically charged substrate and the through thin joints of epoxy adhesive between two
oppositely charged columns that extend into the bulk copper cylinders, it was observed, after separating the
of the adhesive. This would also account for the substrates, that the interface between the copper and
electrostatic interactions supposed to contribute to
adhesion, which, by their very nature, are water
sensitive. ku(v)
The existence of charge columns also explains the
origin of conduction in thin joints 8, and the exo-
emission of charge upon fracture 9" l0
5 I0
Columnar structure of the interface ' X m
By ionic etching of the cross-section of an aluminium/ d(pm)
epoxy joint, KOtting II revealed a fine structure inside
the polymeric interface that comprised a dense network
of columns originating from the aluminium layer and
extending over a length of 5 p m (Fig. 4). We observed -0.4 X
cellular structure to the same depth with the ultrasonic
microscope.

Charges in m e t a l / p o l y m e r interfaces
-0.8 X--X,
The aluminium/polyethylene interface
Possart 12 studied the electrical potential distribution in Fig. 5 The electrical potential distribution in the polyethylene/aluminium
interphase. A diffuse layer of negative charges spreads over 10/~ m from
the aluminium/polyethylene interface by recording the the interface

INT.J.ADHESION AND ADHESIVES APRIL 1991 11 5


Fig. 6 Scanning electron micrograph showing that in thin joints the
columns initiated from the surfaces merge into one channel crossing the
polymeric layer (Kotting ~1 with permission)
the epoxy resin was blue, indicating the presence of
copper ions in the interface over a length of 1-2 urn.
Analysis by atomic absorption spectroscopy gave a
weight of copper ions of 27 × 10 -t' g for two interfaces
of 1 cm-'. The dissolution of zinc. aluminium and lead
in the interface between galvanized steel (where A[ and
Pb are incorporated in the zinc layer to obtain special
properties) and epoxy resin has been obse~'ed by
X-ray photoelectron spectroscopy H,
This dissolution of substrate in the adhesive is often
neglected in the identification of the locus of fracture
of adhesive bonds and may lead to erroneous
conclusions in the assignment of its place in the
interphase.
Electrical conduction in thin adhesive joints
It has been observed that thin (10-20,u m) adhesive
joints enclosed between metallic surfaces become
electrically conductive s. One way to explain that
conduction would be to assume that charges adsorbed
at the solid/liquid adhesive interlace spread through
the adhesive layer and ensure electrical conduction by
electron hopping.
However, the charge density' at a solid/liquid
interface is about 100 times that of the bulk tS. This
charge concentration would be too low in epoxy resins,
which have a resistivity around 105 ~ cm s, to account
tbr the number of charges necessau to make the
adhesive film conductive. This observation led to the
assumption that there were conductive channels inside
the metal/adhesive interphase where the charge
116 INT.J.ADHESION A N D ADHESIVES APRIL 1 991
concentration was high. When the adhesive joi,lt is
thin the channels originating from both surfaces merge
and ensure electrical conduction. These channels could
be those observed by Krtting It (or the cell walls
observed in the at, thor's previous work) that have been
shown to merge in thin joints (Fig. 6).
Conclusions
From the above results the following picture of the
metal/polymer interface in an adhesive-bonded joint
may be drawn.
I) There are nodules of polymeric materials separated
by walls.
2) The interphase contains injected electrons.
3) The interphase contains ions dissolved from the
substrate.
4) Columns initiating from the surlace merge in thin
joints.
5) When the two interphases encounter one another,
the thin joint conducts electricity.
References
1 Sharpe, L. Adhesion Society Short Course (1985)
2 Brockmann, W. Mat~r/aux et Techniques "Specia/Collage"
(December 1988)
3 Schultz. J. SOC Fr Vide Course on Adherence (1987)
4 CuthrelI, R.E. J A p p / P o l y m S c i 1 1 (1967) p p 9 4 9 - 9 5 2
5 Cognard, J. J Adhesion 26 (1988) pp 155-169
6 Cognard, J., Sattish, S., Kullick, A. and Gremaud, G. submitted to
J Adhesion
7 Comyn, J. Plast Rubber Proc A p p / 3 (1983) pp 201-205
8 Cognard, J. Le Vide les couches minces 246 (1989) pp 261-272
9 Dickinson, J.T. and Krasto, A.S. in "Cross/inked Polymers" edited
by R.A. Dickic (ACS 367, 1988) pp 145-188
10 Viskne, A.V., Kalnin, M.M., Kranya, U.E., Pitis, Z.T.U., Ozolin'sh,
Yu.L, and Tutans, M.Ya. Mekhanika Kompositnykh Materialow 6
(1983) pp 1099-1102 (English Translation 812-815)
11 Hahn, O. and Kotting, G. Schweissen und Schneiden 36 (1984)
p6
12 Possart, W . / n t J Adhesion and Adhesives 8 (1988) pp 77-84
13 Lavielle, L., Prev6t, J.L. and Schultz, J. Ang Makromol Chem 169
(1989) p p 1 5 9 - 1 7 4
14 Maeda, S., Assai, T., Fujii, S., Nomura, Y. and Nomoka, A. Polym
Mater Sci Engng 58 (1988) pp 32-36
15 Mohilner, D. in "Advances in Elecrroanalytical Chemistry" edited by
A J. Bard (Marcel Dekker, NY, 1966) p 249 ff
Author
Dr Cognard, who is with Asulab SA, can be contacted
at Serroue 17, CH-2006 Neuch~tel, Switzerland.