Nanostructured polymers for photonics

We review recent progress in the development of polymer nanostructured materials with periodic structures and compositions having applications in photonics and optical data storage. This review provides a brief description of the microfabrication and self-assembly methods used for the production of polymer materials with periodic structures, and highlights the properties and applications of photonic materials derived from block copolymers, colloid crystals, and microfabricated polymers. We conclude with a summary of current and future research efforts and opportunities in the development of polymer materials for photonic applications

Phytoglycogen nanoparticles : nature-derived superlubricants

Phytoglycogen nanoparticles (PhG NPs), a single-molecule highly branched polysaccharide, exhibit excellent water retention, due to the abundance of close-packed hydroxyl groups forming hydrogen bonds with water. Here we report lubrication properties of close-packed adsorbed monolayers of PhG NPs acting as boundary lubricants. Using direct surface force measurements, we show that the hydrated nature of the NP layer results in its striking lubrication performance, with two distinct confinement-controlled friction coefficients. In the weak- to moderate-confinement regime, when the NP layer is compressed down to 8% of its original thickness under a normal pressure of up to 2.4 MPa, the NPs lubricate the surface with a friction coefficient of 10–3. In the strong-confinement regime, with 6.5% of the original layer thickness under a normal pressure of up to 8.1 MPa, the friction coefficient was 10–2. Analysis of the water content and energy dissipation in the confined NP film reveals that the lubrication is governed by synergistic contributions of unbound and bound water molecules, with the former contributing to lubrication properties in the weak- to moderate-confinement regime and the latter being responsible for the lubrication in the strong-confinement regime. These results unravel mechanistic insights that are essential for the design of lubricating systems based on strongly hydrated NPs

One-step fabrication of microchannels with integrated three dimensional features by hot intrusion embossing

We build on the concept of hot intrusion embossing to develop a one-step fabrication method for thermoplastic microfluidic channels containing integrated three-dimensional features. This was accomplished with simple, rapid-to-fabricate imprint templates containing microcavities that locally control the intrusion of heated thermoplastic based on their cross-sectional geometries. The use of circular, rectangular and triangular cavity geometries was demonstrated for the purposes of forming posts, multi-focal length microlense arrays, walls, steps, tapered features and three-dimensional serpentine microchannels. Process variables, such as temperature and pressure, controlled feature dimensions without affecting the overall microchannel geometry. The approach was demonstrated for polycarbonate, cycloolefin copolymer and polystyrene, but in principle is applicable to any thermoplastic. The approach is a step forward towards rapid fabrication of complex, robust, microfluidic platforms with integrated multi-functional elements

Colloidal analogs of molecular chain stoppers

Self-assembly of nanoparticles in polymer-like chains bears a strong similarity to polymerization reactions, in which monomer units are brought together by directional noncovalent interactions. Based on this similarity, the molecular concepts of polymer chemistry can be applied to achieve controllable nanoparticle assembly. On the other hand, the ability to visualize nanoparticle assemblies and to exploit characterization tools used in nanoscience offers a unique way to study polymerization reactions. Here we explore this twofold strategy for an exemplary system including the self-assembly of bifunctional metal nanorods in the presence of monofunctional nanoparticles (chain stoppers). The approach provided insight into the polymerization kinetics, side reactions, the distribution of species in the system, and the design rules for the synthesis of molecular chain stoppers

Step-Growth Polymerization of Inorganic Nanoparticles

Self-organization of nanoparticles is an efficient strategy for producing nanostructures with complex, hierarchical architectures. The past decade has witnessed great progress in nanoparticle self-assembly, yet the quantitative prediction of the architecture of nanoparticle ensembles and of the kinetics of their formation remains a challenge. We report on the marked similarity between the self-assembly of metal nanoparticles and reaction-controlled step-growth polymerization. The nanoparticles act as multifunctional monomer units, which form reversible, noncovalent bonds at specific bond angles and organize themselves into a colloidal polymer. We show that the kinetics and statistics of step-growth polymerization enable a quantitative prediction of the architecture of linear, branched, and cyclic self-assembled nanostructures; their aggregation numbers and size distribution; and the formation of structural isomers

Structural Transitions in Nanoparticle Assemblies Governed by Competing Nanoscale Forces

Assembly of nanoscale materials from nanoparticle (NP) building blocks relies on our understanding of multiple nanoscale forces acting between NPs. These forces may compete with each other and yield distinct stimuli-responsive self-assembled nanostructures. Here, we report structural transitions between linear chains and globular assemblies of charged, polymer-stabilized gold NPs, which are governed by the competition of repulsive electrostatic forces and attractive poor solvency/hydrophobic forces. We propose a simple quantitative model and show that these transitions can be controlled by the quality of solvent, addition of a salt, and variation of the molecular weight of the polymer ligands