Current Nanoscience, 2006, 2, 351-357 351
1573-4137/06 $50.00+.00 © 2006 Bentham Science Publishers Ltd.
Stress-Induced Reduction of Water Uptake in Clay-reinforced Epoxy
Nanocomposites
Erol Sancaktar* and Jason Kuznicki
Department of Polymer Engineering, The University of Akron, Akron, OH 44325, USA
Abstract: Exfoliated nano-clay/epoxy composites typically contain approximately 1 nm thick layers of clay
dispersed in the polymer matrix. Owing to the platy morphology of the silicate layers, exfoliated clay
nanocomposites can exhibit dramatically improved barrier and mechanical properties that are not available with
conventional composite materials. Since epoxy applications may exist in areas of high moisture content and under
mechanically induced stress, the effect of such stressing on water uptake by epoxy-clay nanocomposites is of
interest. In this work, low viscosity liquid aromatic diglycidyl ether of bisphenol A (DGEBA) epoxy resin, Epon
815C, was mixed with Montmorillonite nanoclay to produce an exfoliated clay – epoxy resin system containing
0.5% nanoclay by weight. These samples were immersed in water in stressed condition (flexural stress) to assess the
effect of stress on the nanocomposite epoxy system’s water uptake behavior. Application of the flexural stress
affected the water uptake barrier properties for the nanoclay/epoxy nanocomposites, with the stress acting to
decrease the rate of absorption as well as to decrease the equilibrium moisture content in the 0.5% loaded
nanocomposite. The results revealed up to 33% reduction in water uptake for the stressed samples.
Keywords: Epoxy nanoclay composites, Nanocomposite barrier properties, Water uptake, Stress effect.
INTRODUCTION
The use of organically modified nanoclays, or organoclays
incorporated into epoxy systems has sparked new interest in
creating better epoxy systems. In incorporating nanoclay
particles into thermoset epoxy resins, the chemical
crosslinking which changes the conformation of the molecule
chains is the key. As the number of bonds between chains
increases, the inter-chain distance decreases causing shrinkage
in the bulk system with an overall increase in chain length as
well as the formation of a three dimensional network. Park
and Jana [1] report that this entropy change and the resulting
elastic forces drive the exfoliation and intercalation in
nanoclay epoxies. The successes and benefits shown by
many others in this area are summarized in a recent review of
the methods and properties of exfoliated polymer-clay
nanocomposites [2].
Models that consider how the addition of nanoclay
benefits moisture diffusion through polymers have surfaced
in the work of Yano, Usuki, Okada, Toshio and Kamigaito
[3] and Drozdov, Christiansen, Gupta and Shah [4]. The
main difference in the theories is the concept of interaction of
water molecules with the clay layers. Yano, Usuki, Okada,
Toshio and Kamigaito assumed no interaction between the
clay in the nanocomposite and water molecules diffusing
through it. Drozdov, Christiansen, Gupta and Shah,
however, assumed a hydrophilic clay particle that attracts and
immobilizes water molecules onto its surface. Many
applications involve epoxy systems under stress and in
humid areas. The protection of the adherend-adhesive
*Address correspondence to this author at the Department of Polymer
Engineering, The University of Akron, Akron, OH 44325, USA; Tel: 330-
972-5508; Fax: 330-258-2339; E-mail: erol@uakron.edu
interface from moisture is a key part to the stability of the
joint. The study aims to compare moisture diffusion through
nanoclay filled epoxy systems in stressed and unstressed
modes. The degree of exfoliation, dispersion, and orientation
of the dispersed clay phase in a stressed and unstressed
epoxy matrix will be characterized by x-ray diffraction and
TEM to provide supporting evidence for our moisture
diffusion findings.
EXPERIMENTAL METHODS AND MATERIALS
Epon 815C supplied by Resolution Performance Products
in Houston, Texas was combined with 30B Montmorillonite
nanoclay from Southern Clay Products (Gonzales, Texas).
The curing agent used was Epi-cure 3223, or Diethylenetri-
amine (DETA) also by Resolution Performance Products.
Low viscosity (5-7 Poise) liquid aromatic diglycidyl ether of
bisphenol A (DGEBA) epoxy resin, Epon 815C, was mixed
with nanoclay at 60°C for 6 hours. The epoxy-clay mixture
was then mixed with curing agent DETA (Diethylenetri-
amine) at 80°C for 4 minutes. Film samples for testing were
cast using a Teflon and PET compression mold. The
nanoclay-filled and neat uncured epoxy systems prepared
were poured into the mold and allowed to gel while under
34.5 MPa of pressure to ensure an average thickness of 0.15
mm. The samples gelled at room temperature, then were
removed and cured at 120°C for 3 hours. The film samples
were cut and then sanded to remove any cracks or chips with
400 grit sandpaper into 2 cm by 3 cm rectangles prior to
testing. Unstressed samples were secured by a weight to a
flat aluminum surface and stressed samples were secured by
plastic clips to aluminum cylinders to induce flexural stress
in such a way that the inner surface under compression was
not exposed to water. The applied stress levels were
determined by the diameter of the cylinders used, and