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Craig J Hawker

Publications and source records attributed to Craig J Hawker.

30 records · Page 2Linked to original sources
PubMed2005

Conformation of intramolecularly cross-linked polymer nanoparticles on solid substrates.

The conformation of cross-linked, monomolecular, polystyrene nanoparticles on a solid substrate is considered as a function of cross-linking degree and substrate surface free energy. It is found that an extreme amount of cross-linking is necessary for the ca. 5-10 nm diameter nanoparticles to retain their original spherical shape, regardless of surface free energy. A lesser amount of cross-linking produces a nanoparticle that collapses to a pancake-like conformation on a high-energy substrate yet remains spherical on a low-energy surface. A simple model is developed to reveal the relationship between nanoparticle modulus and surface free energy to define the nanoparticle conformation.

Journal Article↗
PubMed2004

Dendronized linear polymers via "click chemistry".

Dendronized linear polymers are prepared from dendritic azides and poly(vinylacetylene) using "click chemistry." The Cu(I)-catalyzed Huisgen [2 + 3] cycloaddition is quantitative up to the third generation.

Journal Article↗
PubMed2003

Nanoscale effects leading to non-Einstein-like decrease in viscosity.

Nanoparticles have been shown to influence mechanical properties; however, transport properties such as viscosity have not been adequately studied. This might be due to the common observation that particle addition to liquids produces an increase in viscosity, even in polymeric liquids, as predicted by Einstein nearly a century ago. But confinement and surface effects provided by nanoparticles have been shown to produce conformational changes to polymer molecules, so it is expected that nanoparticles will affect the macroscopic viscosity. To minimize extraneous enthalpic or other effects, we blended organic nanoparticles, synthesized by intramolecular crosslinking of single polystyrene chains, with linear polystyrene macromolecules. Remarkably, the blend viscosity was found to decrease and scale with the change in free volume introduced by the nanoparticles and not with the decrease in entanglement. Indeed, the entanglements did not seem to be affected at all, suggesting unusual polymer dynamics.

Diffusion↗
PubMed2003

A versatile method for tuning the chemistry and size of nanoscopic features by living free radical polymerization.

A novel approach is presented for manipulating the size and chemistry of nanoscopic features using a combination of contact molding and living free radical polymerization. In this approach a highly cross-linked photopolymer, based on a methacrylate/acrylate mixture, was patterned into submicrometer-sized features on a silicon wafer using a contact-molding technique. A critical component of the monomer mixture was the incorporation of an initiator containing monomer into the network structure, which provides sites for functional group amplification. Features ranging in size from 5 microm to <60 nm were accurately replicated by this process and living free radical polymerizations, both atom transfer radical and nitroxide-mediated polymerization (NMP), could be conducted from these initiating sites to yield polymer brushes which represent a grafted layer of linear chains attached to the original network polymer. Grafts consisting of polystyrene, poly(methyl methacrylate), and poly(2-hydroxyethyl)methacrylate were grown with controlled thicknesses ranging from 10 to 143 nm and graft molecular weights of between 18 000 to 290 000 amu. As a result of this secondary graft process, feature sizes could be tuned from the original 100 nm down to 20 nm, and the surface chemistry varied from hydrophilic to hydrophobic starting from the same initial master pattern. The thin films and patterned features were characterized by contact angle, ellipsometry, optical, and atomic force microscopies.

Journal Article↗
PubMed2003

A modular approach toward functionalized three-dimensional macromolecules: from synthetic concepts to practical applications.

A new strategy for the preparation of functional, multiarm star polymers via nitroxide-mediated "living" radical polymerization has been explored. The generality of this approach to the synthesis of three-dimensional macromolecular architectures allows for the construction of nanoscopically defined materials from a wide range of different homo, block, and random copolymers combining both apolar and polar vinylic repeat units. Functional groups can also be included along the backbone or as peripheral/chain end groups, thereby modulating the reactivity and polarity of defined portions of the stars. This modular approach to the synthesis of three-dimensional macromolecules permits the application of these tailored materials as multifunctional hosts for hydrogen bonding, nanoparticle formation, and as scaffolds for catalytic groups. Examples of applications of the functional stars in catalysis include their use in a Heck-type coupling as well as an enantioselective addition reaction.

Journal Article↗
PubMed2002

Application of complex macromolecular architectures for advanced microelectronic materials.

The distinctive features of well-defined, three-dimensional macromolecules with topologies designed to enhance solubility and amplify end-group functionality facilitated nanophase morphologies in mixtures with organosilicates and ultimately nanoporous organosilicate networks. Novel macromolecular architectures including dendritic and star-shaped polymers and organic nanoparticles were prepared by a modular approach from several libraries of building blocks including various generations of dendritic initiators and dendrons, selectively placed to amplify functionality and/or arm number, coupled with living polymerization techniques. Mixtures of an organosilicate and the macromolecular template were deposited, cured, and the phase separation of the organic component, organized the vitrifying organosilicate into nanostructures. Removal of the sacrificial macromolecular template, also denoted as porogen, by thermolysis, yielded the desired nanoporous organosilicate, and the size scale of phase separation was strongly dependent on the chain topology. These materials were designed for use as interlayer, ultra-low dielectric insulators for on-chip applications with dielectric constant values as low as 1.5. The porogen design, chemistry and role of polymer architecture on hybrid and pore morphology will be emphasized.

Electronics↗
PubMed2002

A facile approach to architecturally defined nanoparticles via intramolecular chain collapse.

A novel approach is presented for the controlled intramolecular collapse of linear polymer chains to give well-defined single-molecule nanoparticles whose structure is directly related to the original linear polymer. By employing a combination of living free radical polymerization and benzocyclobutene (BCB) chemistry, nanoparticles can be routinely prepared in multigram quantities with the size being accurately controlled by either the initial degree of polymerization of the linear chain or the level of incorporation of the BCB coupling groups. The latter also allows the cross-link density of the final nanoparticles to be manipulated. In analogy with dendritic macromolecules, a significant reduction of up to 75% in the hydrodynamic volume is observed on going from the starting random coil linear chains to the corresponding nanoparticles. The facile nature of the living free radical process also permits wide variation in monomer selection and functional group incorporation and allows novel macromolecular architectures to be prepared. Furthermore, the use of block copolymers functionalized with benzocyclobutene groups in only one of the blocks gives, after intramolecular collapse, a hybrid architecture in which a single linear polymer chain is attached to the globular nanoparticle.

Acrylic Resins↗
PubMed2002

The effect of macromolecular architecture in nanomaterials: a comparison of site isolation in porphyrin core dendrimers and their isomeric linear analogues.

The influence of macromolecular architecture on the physical properties of polymeric materials has been studied by comparing poly(benzyl ether) dendrons with their exact linear analogues. The results clearly confirm the anticipation that dendrimers are unique when compared to other architectures. Physical properties, from hydrodynamic volume to crystallinity, were shown to be different, and in a comparative study of core encapsulation in macromolecules of different architecture, energy transduction from the polymer backbone to a porphyrin core was shown to be different for dendrimers as compared to that of isomeric four- or eight-arm star polymers. Fluorescence excitation revealed strong, morphology dependent intramolecular energy transfer in the three macromolecular isomers investigated. Even at high generations, the dendrimers exhibited the most efficient energy transfer, thereby indicating that the dendritic architecture affords superior site isolation to the central porphyrin it surrounds.

Journal Article↗