Tetramethylammonium silanolate-initiated ring-opening copolymerization of octamethylcyclotetrasiloxane (D(4)) and bis(heptamethylcyclotetrasiloxanyl)ethane (bis-D(4)) renders cross-linked network polymers that contain ethylene bridges and active silanolate end groups. These "living" reactive anionic species are not neutralized by ambient atmosphere exposure (are stable to water, oxygen, CO(2)) and promote thermally activated equilibration among different network isomers and cyclic oligomers. The cross-link density of these living networks can be controlled by the ratio of D(4):bis-D(4), and the density of active chain ends is determined from the initiator:monomer ratio. We report that samples prepared with particular ratios of initiator:D(4):bis-D(4) can be cut with a sharp knife, even into two pieces, and can heal by siloxane equilibration to restore the original strength of the silicone sample. Fracture toughness measurements were carried out and revealed complete (mechanical) healing. Broken and healed samples generally failed in locations other than the initially cracked region. We call attention to publications and patents from the 1950s that suggest that this self-healing behavior was likely obvious 60 years ago.

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We demonstrate the preparation of extremely cross-linked poly(dimethylsiloxane) (PDMS)-based materials and report optical, mechanical, and surface properties. Transparent monolithic molded objects are prepared catalytically with no byproducts; parts per million levels of platinum (catalyst) remain in the articles. Essentially the same material was prepared in 1993 and described as a "hard transparent glass." We confirm the thermal stability and chemical structure described in this report. We show that the catalytic reaction used, which was reported in 1999 always to exhibit a "violent exotherm", can be controlled conveniently using a low (parts per million) catalyst concentration. The combination of low surface energy, transparency, hardness, elasticity, and thermal stability makes this an unusual and interesting material. That it can be prepared from commercially available low-viscosity monomers adds to its interest. We comment that the class of materials known as siloxanes or silicones and PDMS in particular is not currently generally well understood (or taught) and review aspects of the structure, properties, and cross-linking chemistry of PDMS.

Silicon/silicon dioxide surfaces containing 3 μm (width) × 6 μm (length) × 40 μm (height) staggered rhombus posts were prepared using photolithography and hydrophobized using a perfluoroalkyl-containing monofunctional silane. These surfaces exhibit water contact angles of θ(A)/θ(R) = 169°/156°. Water drops come to rest on a carefully aligned horizontal sample but roll when the surface is tilted slightly. No visible trail or evidence of water "left behind" at the receding edge of the drop is apparent on surfaces that water drops have rolled on or on samples removed from water through the air-water interface. When dimethylbis(β-hydroxyethyl)ammonium methanesulfonate (N(+)S(-), a nonvolatile ionic liquid) is used as the liquid probe fluid (instead of water), contact angles of θ(A)/θ(R) = 164°/152° are observed and ∼3-μm-diameter sessile drops are visible (by scanning electron microscopy - SEM) on the top of every post of a sample drawn out of this liquid. We interpret the formation of these sessile microdrops as arising from microcapillary bridge failure that occurs during receding events and emphasize that the capillary bridges rupture in primarily a tensile failure mode. Smaller sessile drops could be prepared using mixtures of water and N(+)S(-). Microdroplets of N(+)S(-) were also observed to form selectively at particular features on surfaces containing square holes separated by ridges. This suggests that pinning sites can be identified using microscopy and this ionic liquid probe fluid.

Template synthesis of various morphological gold colloidal nanoparticles using a thermoresponsive and pH-responsive coordination triblock copolymer of poly(ethylene glycol)-b-poly(4-vinylpyridine)-b-poly(N-isopropylacrylamide) is studied. The template morphology of the thermoresponsive and pH-responsive coordination triblock copolymer, which can be tuned by simply changing the pH or temperature of the triblock copolymer aqueous solution, ranges from single chains to core-corona micelles and further to micellar clusters. Various morphological gold colloidal nanoparticles such as discrete gold nanoparticles, gold@polymer core-shell nanoparticles, and gold nanoparticle clusters are synthesized on the corresponding template of the triblock copolymer by first coordination with gold ions and then reduction by NaBH4. All three resultant gold colloidal nanoparticles are stable in aqueous solution, and their sizes are 2, 10, and 7 nm, respectively. The gold@polymer core-shell nanoparticles are thermoresponsive. The gold nanoparticle cluster has a novel structure, and each one holds about 40 single gold nanoparticles.