Randall S. Saunders

The ordering of symmetric diblock copolymers: A comparison of self-consistent-field and density functional approaches

Polymer reference interaction site model (PRISM) based density functional (DF) theory is used to evaluate the structure and thermodynamics of structurally symmetric, freely jointed, diblock chains with 0.50 volume fraction. These results are compared to the results of self-consistent-field (SCF) theory. Agreement between the predictions of the SCF and DF theories is found for the lamella spacing well above the order–disorder transition (ODT) and for the qualitative behavior of the interfacial thickness as a function of both chain length and Flory–Huggins χ parameter. Disagreement is found for the magnitude of the interfacial thickness where DF theory indicates that the thickness is 1.7±0.2 times larger than that predicted by SCF theory. It appears that behavior on the monomer length scale is sensitive to system specific details which are neglected by SCF theory.

The interfacial thickness of symmetric diblock copolymers: Theory and experiment

A recent application of density functional theory to the structure and thermodynamics of the ordering of symmetric, tangent hard site, diblock copolymers [S. K. Nath et al., J. Chem. Phys. 106, 1950 (1997)] predicted an interfacial thickness larger than would be expected from previous self-consistent-field studies of thread chains. Here we compare the theoretical predictions with the few experimental measurements of interfacial thickness in symmetric diblocks. It is observed that predictions of the thickness of the interface are sensitive to the details of the monomer structure included in the underlying model, and that the range of the experimental measurements is spanned by the two theoretical models.

LDRD final report on intelligent polymers for nanodevice performance control

A variety of organic and hybrid organic-inorganic polymer systems were prepared and evaluated for their bulk response to optical, thermal and chemical environmental changes. These included modeling studies of polyene-bridged metal porphyrin systems, metal-mediated oligomerization of phosphaalkynes as heteroatomic analogues to polyacetylene monomers, investigations of chemically amplified degradation of acid- and base-sensitive polymers and thermally responsive thermoplastic thermosets based on Diels-Alder cycloaddition chemistry. The latter class of materials was utilized to initiate work to develop a new technique for rapidly building a library of systems with varying depolymerization temperatures.

Final report for the designed synthesis of controlled degradative materials LDRD

The main goal of this research was to develop degradable systems either by developing weaklink-containing polymers or identifying commercial polymeric systems which are easily degraded. In both cases, the degradation method involves environmentally friendly chemistries. The weaklinks are easily degradable fragments which are introduced either randomly or regularly in the polymer backbone or as crosslinking sites to make high molecular weight systems via branching. The authors targeted three general application areas: (1) non-lethal deterrents, (2) removable encapsulants, and (3) readily recyclable/environmentally friendly polymers for structural and thin film applications.

Preparation and characterization of phenyl-, benzyl-, and phenethyl-substituted polysilsesquioxanes

Polysilsesquioxanes are a class of siloxane polymers commonly prepared by the hydrolysis and condensation of trialkoxysilanes or trichlorosilanes. From a trifunctional monomer one would expect the organically-modified polymers to be highly crosslinked and insoluble resins. However, while some silsesquioxane monomers with R = H, CH{sub 3}, or vinyl do form crosslinked polymers capable of forming gels, the majority react to form soluble oligosilsesquioxanes, including discrete polyhedral oligomers, and polymers. Because of their solubility, ladder structures have been proposed. However, viscosity studies by Frye indicate that the polyphenylsilsesquioxane is more likely best represented by a polymer rich in both cyclic structures and branches, but without any regular stereochemistry. In this study, the authors have examined the hydrolysis and condensation polymerizations of phenyltrialkoxysilane, benzyltrialkoxysilane, and 2-phenethyltrialkoxysilane monomers under both acidic and basic conditions. The resulting phenyl, benzyl and phenethyl-substituted polysilsesquioxanes were characterized by {sup 1}H, {sup 13}C, {sup 29}Si NMR, gel permeation chromatography, and differential scanning calorimetry. The effects of the organic substituent (phenyl, benzyl, phenethyl), alkoxide group (OMe, OEt), catalyst (HCl, NaOH), monomer concentration, and polymer processing on polymer molecular weight and glass transition temperature were determined.

Adhesive Systems Based on Functionalized Block Copolymers

Functionalized block copolymers were synthesized as adhesion promoters using Ring-Opening Metathesis Polymerization (ROMP). They were designed for glass/epoxy and copper/epoxy interfaces. The former contained triethoxysilane groups in the first block and secondary amine groups in the second. The latter contained imidazole groups in the first and amine groups in the second block. These block copolymers were shown to form ordered monolayers on the respective glass and copper surfaces using neutron reflectivity. Adhesion measurements showed an enhancement of adhesion after application of these block copolymers.