The atom transfer radical polymerization of octadecyl acrylate (ODA) has been investigated and optimized to produce polymers with predetermined molecular weights and narrow polydispersities (Ͻ1.2). The poor solubility of the catalytic system formed with conventional ligands such as the N-(n-propyl)-2-pyridylmethanimine and 2,2Ј-bipyridine with Cu(I)Br in nonpolar reaction conditions gave poor control over molecular weight characteristics in ODA polymerizations. The use of N-(n-octyl)-2pyridylmethanimine in combination with Cu(I)Br yielded a more soluble catalyst that improved control over the polymerization. The products from the polymerizations were further improved when an initiator, octadecyl 2-bromo-2-methyl-propanoate, similar in structure to the monomer, was used. Together, these modifications produced polymerizations that showed true controlled character as well as products with predetermined molecular weights and narrow polydispersities. Diblock copolymers of PODA were prepared with methyl methacrylate (MMA) and olig(oethylene glycol) methyl ether methacrylate (OEGMA). The PODA-block-POEGMA copolymers are the first examples of all comblike amphiphilic block copolymers. One of PODA-block-POEGMA copolymer samples has been shown to self-assemble as micelles in a dilute aqueous solution.

Waterborne colloidal polymers (i.e. latex) represent a promising alternative to organic solventbased systems in coatings applications. The development of mechanical strength and hardness is often enhanced by chemical crosslinking that creates a threedimensional network. If extensive crosslinking occurs within the particles prior to their coalescence, however, interdiffusion will be prevented. A weaker product will result. We have explored the inter-relationship between coalescence, crosslinking, and surfactant exudation in an acrylic latex containing diacetone acrylamide exploiting the ''keto-hydrazide'' crosslinking reaction. The complementary use of spectroscopic techniques on a model system determined that the crosslinking reaction yields an imine, not an enamine as has been proposed in some literature. Gel fraction measurements were used to probe the rate and amount of crosslinking and identified a slower rate in larger particles, suggesting that the transport of crosslinking agent is rate-limiting. The keto-hydrazide reaction was found to be acid catalyzed and favored at lower water concentration. Measurement of the latex pH relative to the polymer mass fraction during film formation clarified the expected point of onset for crosslinking in relation to particle packing. Atomic force microscopy was used to follow surface leveling relative to the competing influence of crosslinking. The rate and total amount of surfactant exudation were found to be influenced by crosslinking, particle deformability (as determined by the temperature relative to the polymer glass transition temperature), and the evaporation rate (as controlled by the relative humidity). There is evidence that surfactant exudation can be triggered by the particle deformation that occurs at film formation temperatures well above the glass transition temperature.

In this paper, we demonstrate the use of continuous hydrothermal flow synthesis (CHFS) technology to rapidly produce a library of 56 crystalline (doped) zinc oxide nanopowders and two undoped samples, each with different particle properties. Each sample was produced in series from the mixing of an aqueous stream of basic zinc nitrate (and dopant ion or modifier) solution with a flow of superheated water (at 450 °C and 24.1 MPa), whereupon a crystalline nanoparticle slurry was rapidly formed. Each composition was collected in series, cleaned, freeze-dried, and then characterized using analytical methods, including powder X-ray diffraction, transmission electron microscopy, Brunauer-Emmett-Teller surface area measurement, X-ray photoelectron spectroscopy, and UV-vis spectrophotometry. Photocatalytic activity of the samples toward the decolorization of methylene blue dye was assessed, and the results revealed that transition metal dopants tended to reduce the photoactivity while rare earth ions, in general, increased the photocatalytic activity. In general, low dopant concentrations were more beneficial to having greater photodecolorization in all cases.

Continuous hydrothermal flow synthesis (CHFS) has been used as a rapid and clean, synthetic method to produce a range of crystalline nanoparticles in the Ti-Zn-O binary system. The nanopowders were prepared from aqueous solutions of titanium(IV) bis(ammonium lactato)dihydroxide (TIBALD) and hydrated zinc nitrate, respectively, using a CHFS reactor which uses superheated water (at 400 C and 24.1 MPa) as a reagent and crystallizing medium. The resulting nanopowders were heat-treated at 850 C for five hours in air to give photoactive semiconductor mixtures of rutile and zinc oxide and/or zinc titanates. The as-prepared powders and their corresponding heat-treated mixed phase photocatalysts were characterized using powder X-ray synchrotron diffraction, transmission electron microscopy, BET surface area measurement, X-ray photoelectron spectroscopy and UV-Vis spectrophotometry. Because of the interest for these materials in UVA and UVB attenuating materials, the UV-Vis profiles of the nanocomposites and solid solutions were studied. Photocatalytic activity of the samples towards the decolourisation of methylene blue dye was also assessed.

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