IRON COMPOUNDS AS ADHESION PROMOTERS FOR BITUMEN

J. Shim-Ton, S. Varevorakul and R. T. Woodhams

Center for the Study of Materials

University of Toronto
Toronto, Canada, M5S lA4

INTRODUCTION

Asphalt paving composites normally contain about 6 percent of

a bituminous hydrocarbon binder and the remainder an inorganic ag-
gregate comprising particles of sand, crushed rock, limestone or other
minerals which may be indigenous to a particular region. Although .it
is recognized that prolonged exposure of asphalt pavements to mois-
ture can cause a pronounced loss of strength and accelerate the de-
terioration of road surfaces, there does not appear to be any gener-
ally acceptable solution to the problem. 1 ,2

There are, of course, numerous amino-type "anti-stripping"

agents which are commercially available for the prevention of mois-
ture damage but in several publications the effectiveness of these
additives has been questioned since in a few cases the addition of
anti-stripping agents, while initially aiding surface wetting, caused
accelerated stripping in the later stages. 3 The tendency of amine
functional groups to imbibe moisture and spontaneously form emulsi-
fied water droplets was responsible for this accelerated deterior-
ation. Ciplijauskas et a1 4 examined the flexural strength of asphalt
concretes in which the ashpalt binder had been chemically modified.
This study concluded that sulfonated or carboxylated asphalts, when
used as binders, can produce composites which are virtually immune
to moisture even after total immersion in water for several months.
However, the results were not uniform and the retention of mechanical
strength was dependent upon the choice of aggregate, most aggregates
being of compiex composition and containing various transition metals,
particularly iron, which could have contributed to the observed
effects. Subsequent contact angle and peel test studies by Shim-Tons

391

J. E. Kresta (ed.), Polymer Additives

© Plenum Press, New York 1984
392 J. SHIM-TON ET AL.

revealed that polar hydrophilic substituents (sulfonic acids, car-

boxyls) were easily displaced by water when such acidic groups were
not insolubilized or complexed with transition metals such as iron
or chromium. Magnesium or calcium salts appear to have an intermedi-
ate adhesion retention and are not as effective for resisting mois-
ture attack.

The use of silane coupling agents as adhesion promoters for

glass fiber reinforced plastics is well known, particularly as a
treatment to minimize the harmful effects of moisture. Morris and
Di Vito 6 were able to demonstrate that silane treatment greatly in-
creased the moisture resistance of asphalt paving composites. Al-
though silanes are certainly effective reagents for protecting asphalt
concretes from moisture, their high cost is likely to deter widespread
application.

In 1970, Fromm observed that a particular reddish-brown aggre-

gate, which was used to pave a section of highway in northern Ontario,
was unusually resistant to moisture damage and more durable than
previous paving surfaces in that region. Subsequent laboratory in-
vestigation 3 revealed that iron naphthenate (or ferric complexes of
1,2-pentanedione) when added to asphalt in minor amounts (1%) were
particularly effective reagents for preventing the loss of adhesion
between asphalt and glass surfaces after immersion in water. The
following investigation was initiated to assess the performance of
iron naphthenate as an anti-stripping agent or coupling agent for
asphalt concrete. Borosilicate glass plates were selected to repre-
sent a typical inorganic substrate and the adhesion of bitumen coat-
ings containing various additives was measured with an ASTM 90 degree
peel test procedure (after a suitable immersion period in distilled
water). The peel test measurements revealed changes taking place in
the cohesive properties of the bitumen during prolonged immersion and
also detected the eventual adhesive failure at any particular temper-
ature.

PREDICTING ADHESION FAILURE

The equilibrium contact angle (8) assumed by liquid bitumen (b)

on a silica surface (s) can be related to the surface energies by
Young's equation

(1)

where Yb = surface free energy of bitumen; Ys = surface free energy

of silica; Ysb = surface free energy of bitumen-silica interface.

The thermodynamic expression for the theoretical work of adhe-

sion Wadh is given by