No abstract

Reversible addition−fragmentation chain transfer (RAFT) solution polymerization is used to prepare well-defined poly(glycerol monomethacrylate) (PGMA) chains bearing carboxylic acid, tertiary amine, or neutral end-groups. Each of these PGMA precursors was then chain-extended in turn via RAFT aqueous emulsion polymerization of 2,2,2-trifluoroethyl methacrylate to form spherical nanoparticles as confirmed by transmission electron microscopy (TEM) analysis. Dynamic light scattering studies indicated an intensity-average diameter of approximately 25 nm. Aqueous electrophoresis measurements confirmed that the amine-functional nanoparticles became cationic at low pH owing to end-group protonation. In contrast, carboxylic acid-functional nanoparticles became appreciably anionic at pH 10 owing to end-group ionization. Finally, nanoparticles bearing neutral end-groups exhibited zeta potentials close to zero over a range of solution pH. High-shear homogenization of n-dodecane in the presence of such sterically stabilized nanoparticles led to the formation of oil-in-water Pickering macroemulsions with volume-average diameters of 20− 30 μm. High-pressure microfluidization was then used to prepare the three corresponding Pickering nanoemulsions. Each Pickering nanoemulsion was characterized by analytical centrifugation and TEM studies of the dried nanoemulsion droplets confirmed their original nanoparticle superstructure. The nanoparticle adsorption efficiency at the oil−water interface was assessed by gel permeation chromatography (using a UV detector) for each nanoparticle type at both pH 3 and 7. Nanoparticles with charged end-groups exhibited relatively low adsorption efficiency, whereas up to 90% of the neutral nanoparticles were adsorbed onto the oil droplets. This observation was supported by small-angle X-ray scattering experiments, which indicated that the packing efficiency of neutral nanoparticles around oil droplets was higher than that of nanoparticles bearing charged end-groups. Analytical centrifugation was used to evaluate the colloidal stability of the aged Pickering nanoemulsions. Pickering nanoemulsions stabilized with nanoparticles bearing charged end-groups proved to be significantly less stable than those prepared using neutral end-groups.

Polyaromatic hydrocarbons (PAHs) are found throughout the universe. The ubiquity of these organic molecules means that they are of considerable interest in the context of cosmic dust, which typically travels at hypervelocities (>1 km s –1 ) within our solar system. However, studying such fast-moving micrometer-sized particles in laboratory-based experiments requires suitable synthetic mimics. Herein, we use ball-milling to produce microparticles of anthracene, which is the simplest member of the PAH family. Size control can be achieved by varying the milling time in the presence of a suitable anionic commercial polymeric dispersant (Morwet D-425). These anthracene microparticles are then coated with a thin overlayer of polypyrrole (PPy), which is an air-stable organic conducting polymer. The uncoated and PPy-coated anthracene microparticles are characterized in terms of their particle size, surface morphology, and chemical structure using optical microscopy, scanning electron microscopy, laser diffraction, aqueous electrophoresis, FT-IR spectroscopy, Raman microscopy, and X-ray photoelectron spectroscopy (XPS). Moreover, such microparticles can be accelerated up to hypervelocities using a light gas gun. Finally, studies of impact craters indicate carbon debris, so they are expected to serve as the first synthetic mimic for PAH-based cosmic dust.

Epoxy‐functional sterically‐stabilized diblock copolymer nanoparticles (ca. 27 nm) are prepared via RAFT dispersion polymerization in mineral oil. Nanoparticle adsorption onto stainless steel is examined using a quartz crystal microbalance. Incorporating epoxy groups within the steric stabilizer chains results in a two‐fold increase in the adsorbed amount, Γ, at 20 °C (7.6 mg m−2) compared to epoxy‐core functional nanoparticles (3.7 mg m−2) or non‐functional nanoparticles (3.8 mg m−2). A larger difference in Γ is observed at 40 °C; this suggests chemical adsorption of the nanoparticles rather than merely physical adsorption. A remarkable near five‐fold increase in Γ is observed for ca. 50 nm epoxy‐functional nanoparticles compared to non‐functional nanoparticles (31.3 vs. 6.4 mg m−2, respectively). Tribological studies confirm that chemical adsorption of the latter epoxy‐functional nanoparticles leads to a significant reduction in friction between 60 °C and 120 °C.

Well-defined sterically stabilized diblock copolymer nanoparticles of 29 nm diameter are prepared by RAFT aqueous emulsion polymerization of methyl methacrylate using a dithiobenzoate-capped poly(glycerol monomethacrylate) precursor. These nanoparticles are evaluated as a dispersant for the preparation of organic crystalline microparticles via ball milling. This is exemplified for azoxystrobin, which is a broad-spectrum fungicide that is widely used to protect various food crops. Laser diffraction and optical microscopy studies indicate the formation of azoxystrobin microparticles of approximately 2 μm diameter after ball milling for 10 min at 400 rpm. Nanoparticle adsorption at the surface of these azoxystrobin microparticles is confirmed by electron microscopy studies. The extent of nanoparticle adsorption on the azoxystrobin microparticles can be quantified using a supernatant assay based on solution densitometry. This technique indicates an adsorbed amount of approximately 5.5 mg m –2 , which is sufficient to significantly reduce the negative zeta potential exhibited by azoxystrobin. Moreover, this adsorbed amount appears to be essentially independent of the nature of the core-forming block, with similar data being obtained for both poly(methyl methacrylate)- and poly(2,2,2-trifluoroethyl methacrylate)-based nanoparticles. Finally, X-ray photoelectron spectroscopy studies confirm attenuation of the underlying N1s signal arising from the azoxystrobin microparticles by the former adsorbed nanoparticles, suggesting a fractional surface coverage of approximately 0.24. This value is consistent with a theoretical surface coverage of 0.25 calculated from the adsorption isotherm data. Overall, this study suggests that sterically stabilized diblock copolymer nanoparticles may offer a useful alternative approach to traditional soluble copolymer dispersants for the preparation of suspension concentrates affecting the context of agrochemical applications.