Fanny Deplace

Fine Tuning the Adhesive Properties of a Soft Nanostructured Adhesive with Rheological Measurements

The major objective of this article is to present recent advances in the methodology to fine tune the adhesive performance of a PSA. In addition to the so-called Dahlquist criterion requiring a low modulus, we propose two additional rheological predictors of the adhesive properties. The first one is derived from the description of the detachment of a linear elastic layer from a rigid substrate. We made an approximate extension of this analysis to the viscoelastic regime and showed that the transition from interfacial cracks to cavitation and fibrillation can be quantitatively predicted from the easily measurable ratio tan(δ)/G′(ω). If a fibrillar structure is formed, the nonlinear large strain properties become important. We showed that the ability of the fibrils to be stretched before final debonding can be predicted from the analysis of simple tensile tests. The softening, which occurs at intermediate strains, and, more importantly, the hardening which occurs at large strains, can be used to predict the mode of failure and the energy of adhesion. The use of this methodology to tune the PSA structure for a specific application has been illustrated for the special case of wb-PSA made of core-shell particles, and improved adhesive properties on polyethylene surfaces have been obtained.

Effect of a Gradient in Viscoelastic Properties on the Debonding Mechanisms of Soft Adhesives

The effect of a composition gradient along the thickness in soft adhesive films was investigated. The adhesion properties of bilayer films made from acrylic solutions, one layer being more cohesive and the other more dissipative, were studied by performing probe tack experiments. To understand the mechanisms that determine the bulk and the interfacial contributions to the debonding, tests on different surfaces were carried out. The results show that the presence of a composition gradient can enhance the adhesive properties, particularly on a low-energy surface such as polyethylene. On steel, the presence of the thin layer of a more elastic adhesive in contact with the adherent can influence significantly the debonding mechanism, transforming the fracture from cohesive to adhesive.

A comparison of tackified, miniemulsion core-shell acrylic latex films with corresponding particle-blend films: structure-property relationships.

Tackifying resins (TRs) are often added to pressure-sensitive adhesive films to increase their peel strength and adhesion energy. In waterborne adhesives, the TR is dispersed in water using surfactants and then blended with colloidal polymers in water (i.e., latex). In such waterborne systems, there are problems with the colloidal stability and difficulty in applying coatings of the particle blends; the films are often hydrophilic and subject to water uptake. Here, an alternative method of making waterborne, tackified adhesives is demonstrated. The TR is incorporated within the core of colloidal polymer particles via miniemulsion polymerization. Atomic force microscopy (AFM) combined with force spectroscopy analysis reveals there is heterogeneity in the distribution of the TR in films made from particle blends and also in films made from miniemulsion polymers. Two populations, corresponding to TR-rich and acrylic-rich components, were identified through analysis of the AFM force-displacement curves. The nanoscale maximum adhesion force and adhesion energy were found to be higher in a miniemulsion film containing 12 wt % tackifying resin in comparison to an equivalent blended film. The macroscale tack and viscoelasticity are interpreted by consideration of the nanoscale structure and properties. The incorporation of tackifying resin through a miniemulsion polymerization process not only offers clear benefits in the processing of the adhesive, but it also leads to enhanced adhesion properties.

Controlled Sparse and Percolating Cross-Linking in Waterborne Soft Adhesives

The effect of low levels of cross-linking on the adhesive and mechanical properties of waterborne pressure-sensitive adhesives was investigated. We have taken advantage of a core-shell latex particle morphology obtained by emulsion polymerization to create a heterogeneous structure of cross-links without major modification of the monomer composition. The latex particles comprise a shell containing cross-linkable diacetone acrylamide (DAAM) repeat units localized on the periphery of a slightly softer core copolymer of very similar composition. Adipic acid dihydrazide was added to the latex prior to film formation to react with DAAM repeat units and affect interfacial cross-linking between particles in the adhesive films. The honeycomb-like structure obtained after drying of the latex results in a good balance between the dissipative properties required for adhesion and the resistance to creep. The characterization of the mechanical properties of the films shows that the chosen cross-linking method creates a percolating lightly cross-linked network, swollen with a nearly un-cross-linked component. With this cross-linking method, the linear viscoelastic properties of the soft films are nearly unaffected by the cross-linking while the nonlinear tensile properties are greatly modified. As a result, the long-term shear resistance of the adhesive film improves very significantly while the peel force remains nearly the same. A simple rheological model is used to interpret qualitatively the changes in the material parameters induced by cross-linking.