Publications

This article summarizes our investigations of tethered chain systems using Langmuir monolayer of polydimethysiloxane-poly styrene (PDMS-PS) diblock copolymers on organic liquids. In this system, the PDMS block adsorbs to the air surface while the PS block dangles into the subphase liquid. The air surface can be made either repulsive or attractive for the tethered PS chain segments by choosing a subphase liquid which has a surface tension lower or greater than that of PS, respectively. The segment profile of the PS block is determined by neutron reflection as a function of the surface density, the molecular weights of the PS and PDMS blocks, and the solution conditions. We cover the range of reduced surface density (SIGMA) characteristic of the large body of data in the literature for systems of chains tethered onto solid surfaces from dilute solution in good or theta solvent conditions (SIGMA < 12). We emphasize quantitative comparisons with analytical profile forms and scaling predictions. We find that the strong-stretching limit invoked in analytical SCF and scaling theories is not valid over this Z range. On the other hand, over a large portion of this range (SIGMA < 5) tethered layers are well described by a renormalization group theory addressing weakly interacting or noninteracting chains. Simultaneous with the study of the profile form, the free energy of the chains is examined through the surface tension. A strong increase in the surface pressure is observed with increasing surface density which determines the maximum surface density which can be achieved. This apparently nonequilibrium effect is attributed to steric interactions and limited lateral interpenetration. This effect may explain several outstanding discrepancies regarding the adsorption of end-functionalized chains and diblock copolymers onto solid surfaces.

The relationships between the extent of interfacial bonding, energy dissipation mechanisms, and fracture toughness in a glassy adhesive/inorganic solid joint are not well understood. We address this subject with a model system involving an epoxy adhesive on a polished silicon wafer containing its native oxide. The extent of interfacial bonding, and the wetting behavior of the epoxy, is varied continuously using self-assembling monolayers (SAMs) of octadecyltrichlorosilane (ODTS). The epoxy interacts strongly with the bare silicon oxide surface, but forms only a very weak interface with the methylated tails of the ODTS monolayer. We examine the fracture behavior of such joints as a function of the coverage of ODTS in the napkin-ring geometry. Various characterization methods are applied to the ODTS-coated surface before application of the epoxy, and to both surfaces after fracture. The fracture data are discussed with respect to the wetting of the liquid epoxy on the ODTS-coated substrates, the locus of failure, and the energy dissipation mechanisms. Our goal is to understand how energy is dissipated during fracture as a function of interface strength.

Work was performed on seven subtasks. Several of these ended before the close of the program. This report contains a summary of each subtask.

We have employed Langmuir monolayer of highly asymmetric polydimethylsiloxane- polystyrene (PDMS-PS) diblock copolymers on dioctyl phthalate (DOP) at temperatures ranging from 22 "C to -35 `C as a model system for tethered chains in poor solvent conditions. The thicknesses of the tethered PS layers extending into the DOP subphase, measured by neutron reflection, decrease with decreasing temperature (T) over this entire r~ge. However, the v~iation with T becomes weak below -20 "C. At the ]owest T, the layer thicknesses are contracted 55 % -75 `% of their values at the theta condition (T8 = 22 "C), but are still quite swollen compared to the fully collapsed, nonsolvent limit. The contraction of the layer with decreasing T is determined as a function of surface density and molecular weight. These data are compared to universal scaling forms. The PS segments are depleted from the air surface over the entire T range, the thickness of the depletion layer increasing slightly with decreasing T. The free energy of the surface layer is probed by surface tension measurements. Negative surface pressures are observed at low coverages for both PDMS-PS and PDMS monolayer, indicating metastability toward lateral phase separation. Evidence for a trruisition from a dispersed phase to a condensed phase with decreasing T was observed in the reflectivity at very low PDMS-PS coverage.

Neutron reflection is used to examine the structure of an epoxy near an interface. Variations in both the density and the crosslink density within the interphase region are examined. The density is increased near the interface relative to that in the bulk of the film, but the crosslink density over the same region is reduced relative to that in the bulk of the film. These observations are interpreted via packing of the resin oligamers next to the wall, which leads to an increased density and also inhibits the crosslinking reaction. The effect is more pronounced the more slowly the resin is cured. Significant variations in reflectivity are observed with thermal cycling, which indicate an increase in the size of the interfacial layer of excess toluene. However, data for samples with greater number of thermal cycles are required to determine the relation of this effect to the fracture process.

It is well known that water plays an important role in the degradation of adhesive strength between a wide variety of materials. It is also well established that silane coupling agents can provide excellent bond durability in aqueous environments. However, the detrimental effects of interfacial water are not limited to adhesive failure. The present study was motivated by concerns in the printed circuit board industry regarding the loss of electrical resistance, as well as adhesive failure, which may arise from water at epoxy/silane/E-glass interphases. The commercial silane finish used in this study provides excellent adhesive strength between epoxy and E-glass, and remarkable bond durability even after extensive conditioning in boiling water or a pressure cooker. However, circuit boards with this finish do not perform well in insulation resistance testing following such conditioning. The goal of this work is to develop a detailed understanding of the mechanism by which water interacts with a resin/silane interphase, with a focus on the consequences for both electrical resistance and adhesion. The present report focuses on the measurement of profiles of adsorbed moisture by neutron reflection.

We are exploring the use of functionalized block copolymers for bonding copper to epoxy in printed wiring boards. Our program involves four key elements: i) synthesis of suitable functionalized block copolymers; ii) characterization of the conformation of the copolymers at the relevant interfaces by neutron reflectivity; iii) spectroscopic measurements of chemical bonding, and iv) measurement of the mechanical properties of the interfaces. The copolymers are synthesized by living, ring-opening metathesis polymerization. This relatively new technique allows great flexibility for synthesis of functionalized block copolymers in that the initiators are relatively insensitive to a wide range of functional groups. Significant adhesion enhancement has been observed in lap shear tests.

The goal of this work is to develop novel functionalized block copolymers to promote adhesion at inorganic substrate/polymer interfaces. We envision several potential advantages of functionalized block copolymers over small molecule coupling agents. Greater control over the structure of the interphase region should result through careful design of the backbone of the copolymer. The number of chains per area, the degree of entanglement between the copolymer and the polymer matrix, the number of sites per chain able to attach to the substrate, and the hydrophobicity of the interphase region can all be strongly affected by the choice of block lengths and the monomer sequence. In addition, entanglement between the copolymer and the polymer matrix, if achieved, should contribute significantly to adhesive strength. Our program involves four key elements: the synthesis of suitable functionalized block copolymers, characterization of the conformation of the copolymers at the interface by neutron reflectivity and atomic force microscopy, characterization of the degree of bonding by spectroscopy, and measurement of the mechanical properties of the interface. In this paper we discuss block copolymers designed as adhesion promoters for the copper/epoxy interface. We have synthesized a diblock with one block containing imidazole groups to bond to copper and a second block containing secondary amines to react with the epoxy matrix. We have also prepared a triblock copolymer containing a hydrophobic middle block. Below we describe the synthesis of the block copolymers by living, ring-opening metathesis polymerization (ROMP) and the first characterization data obtained by neutron reflectivity.

Neutron reflectivity is among the few techniques able to probe a buried interface. Through the use of isotopic labeling, complicated interface structures may be determined with a resolution on the order of 5 {angstrom}. However, for highly complex thin film and interface structures, it is often necessary to perform complementary experiments to reduce the number of unknown variables, and thus enable an unambiguous interpretation of the neutron reflectivity. To this end, the authors have combined X-ray and neutron reflectivity to study changes in a metal/polymer interface (molybdenum/polyurethane, hereafter Mo/PU) upon exposure to a humid environment. In particular, the authors have tracked the adsorption of moisture to the interface and variations in the density of the interphase. This information was obtained as a function of the concentration of a silane coupling agent added to the bulk of the PU. Adhesion of the Mo/PU interface is important to programs in the DOE complex. This paper reports the first results of this study.