Organosilica hybrid films and fluorinated organosilica hybrid films have been successfully deposited using atmospheric plasma deposition. Different precursors, which incorporates epoxy groups in their molecules, were used to obtain connected structures with tunable chemistry and connectivity. The study demonstrated the capability of tuning the chemical composition, connectivity and mechanical properties of organosilica films by selecting the precursors and operational parameters of the process. The use of (3-glycidiloxypropyl) trimethoxysilane (GPTMS) and 2-(3,4-epoxy-cyclohexylethyl) trimethoxysilane (TRIMO) as precursors made possible the deposition of hybrid films with high organic character, increasing the relative C content up to 20 at% and 40 at%, respectively, due to the lower fragmentation caused during the deposition by atmospheric plasma. The obtained structures had higher concentration of symmetric cages than those obtained from precursors without epoxy groups, which lead to a more compact structure and higher stiffness than conventional organic films. The combination with a fluorinated molecule also had a strong influence in the resultant structure caused by the preferential orientation of fluorinated molecules due to the low surface energy of FDTS that causes migration of fluorinated tails to the film-air interface during the film growth.

We demonstrate the deposition of mechanically robust UV-absorbing nanocomposite coatings with a newly developed dual-source deposition method involving ultrasonic spraying and open-air plasma deposition. Nanoparticles and the coating matrix are independently deposited which eliminates difficulties associated with preparing composites with high mass fraction of well-dispersed nanoparticles in the matrix. Nanocomposite coatings containing different concentrations of silica, ceria, and both titania and ceria nanoparticles were successfully deposited with good nanoparticle dispersity, high transparency over the visible range, effective absorption in the UV wavelength, and enhanced mechanical properties. Moreover, films were successfully deposited on several substrates including polycarbonate to demonstrate the low processing temperature of this dual-source deposition method. Coatings with different nanoparticle concentrations and film thicknesses were systematically studied in terms of their surface morphology, optical properties and mechanical properties. Accelerated photostability testing of the UV-absorbing nanocomposites demonstrates significantly enhanced performance compared to existing coatings with either a polymeric matrix or organic UV-absorbers.

The successful processing of bilayer protective coatings on plastics using a combined spray and atmospheric plasma deposition method is shown. The base layer is a spray deposited coating with high adhesion using (3‐glycidyloxypropyl) trimethoxysilane and tetrapropyl zirconate (TPOZ) precursors. The top dense layer is deposited by atmospheric plasma deposition with a tetraethyl orthosilicate precursor. The coating deposition rate, chemical composition, elastic modulus, hardness, and adhesion to poly(methyl methacrylate) (PMMA) substrates are investigated. The adhesion to the polymer substrate is found to decrease with increasing TPOZ content in the precursor solution, while the elastic modulus and hardness of the base layer increase. A silane surface pretreatment of the PMMA substrate is shown to significantly increase the coating adhesion. The adhesion of the optimized coating is so high that it forces the debond interface change from adhesive failure at the coating/PMMA interface to cohesive failure within the PMMA substrate. The combined bilayer structure exhibits a >90% transparency in the visible wavelengths, eightfold increase in adhesion energy and fourfold increase in Young's modulus compared to commercial sol–gel polysiloxane coatings. The approach provides a strategy for an unprecedented combination of adhesion and mechanical properties.

Polymerization-induced self-assembly of 2-hydroxypropyl methacrylate is conducted in water and water/MeOH using a CO2-responsive macroRAFT agent in the form of a statistical copolymer comprising N,N-diethylaminoethyl methacrylate (DEAEMA) and poly(ethylene glycol) methyl ether methacrylate (M-n=475 g mol(-1)). Pressurization with CO2 leads to protonation of DEAEMA units within the stabilizer block, thereby offering a means of adjusting the charge density of the coronal layer. It is demonstrated that a wide range of tunable particle morphologies are accessible by simply varying the CO2 pressure during polymerization in the range of 10-45 bar.

It is demonstrated how the morphology of polymeric nanoparticles produced via polymerization-induced self-assembly (PISA) in dispersion can be conveniently tuned via the pH and ionic strength.

Pressurization of a macroemulsion comprising a vinyl monomer/water/surfactant can result in formation of a transparent miniemulsion without use of high energy mixing, suitable for synthesis of polymeric nanoparticlesviaminiemulsion polymerization.

We demonstrate the deposition of transparent organosilicate protective bilayer coatings on poly methyl methacrylate (PMMA) substrates with different carbon chain length dipodalsilane precursors using atmospheric plasma deposition in ambient air. The bottom adhesive layer was a hybrid organosilicate coating deposited using either only carbon bridge organosilicate precursor or accompanied with a ring structure 1,5-cyclooctadiene precursor. The top layer was a dense silica coating with high elastic modulus and hardness deposited with only carbon bridge precursor. The adhesion energy of bottom layer increased with increasing carbon bridge length of precursors while the density, hardness, and elastic modulus of top hard layer decreased. The deposited bilayer structure showed ∼3 times the adhesion energy and four times the elastic modulus of commercial polysiloxane sol–gel coatings.

We demonstrate a dual organic and inorganic precursor method to deposit transparent organosilicate protective bilayer coatings on poly methyl methacrylate (PMMA) substrates with atmospheric plasma deposition in ambient air. The bottom layer was a hybrid organosilicate adhesive layer deposited with dual organic 1, 5-cyclooctadiene (CYC) and Tetraethoxysiline (TEOS) precursors. The selection of the organic CYC precursor allowed incorporation of carbon chain in the organosilicate adhesive layer, which resulted in improved adhesion. The top layer was a dense silica coating with high Young's modulus and hardness deposited with TEOS. The deposited bilayer structure showed ∼100% transparency in the visible light wavelength region, twice the adhesion energy and five times the Young's modulus of commercial polysiloxane sol-gel coatings.

The synthesis of polymeric nanocapsules in the approximate diameter range 40-100 nm (TEM/SEM) using catanionic surfactant vesicle templates stabilized by subcritical CO2 is demonstrated. Near equimolar aqueous solutions of the surfactants sodium dodecyl sulfate (SDS) and dodecyltrimethylammonium bromide (DTAB) experienced immediate vesicle destabilization and precipitation in the absence of CO2. However, pressurization with CO2 (5 MPa) dramatically enhanced the stability of the initial vesicles, and enabled swelling of the bilayers with hydrophobic monomers via diffusion loading (loading of monomers into preformed bilayers). Subsequent radical crosslinking polymerization of the monomers n-butyl methacrylate/tert-butyl methacrylate/ethylene glycol dimethacrylate contained within the bilayers was conducted at room temperature using UV-initiation under CO2 pressure. The hollow structure of the resultant nano-objects was confirmed by successful encapsulation and retention of the dye Nile Blue. It is demonstrated that using this method, polymeric nanocapsules can be successfully prepared using diffusion loading of up to 94 wt% monomer (rel. to surfactant) stabilized by CO2.

We demonstrate a dual organic and inorganic precursor method to deposit transparent organosilicate protective bilayer coatings on poly methyl methacrylate (PMMA) substrates with atmospheric plasma deposition in ambient air. The bottom layer was a hybrid organosilicate adhesive layer deposited with dual organic 1,5-cyclooctadiene (CYC) and widely used inorganic tetraethoxysiline (TEOS) precursors. The selection of the organic CYC precursor allowed incorporation of a carbon chain in the organosilicate adhesive layer, which resulted in improved adhesion. The top layer was a dense silica coating with high Young's modulus and hardness deposited with TEOS. The deposited bilayer structure showed ∼100% transparency in the visible light wavelength region, twice the adhesion energy, and five times the Young's modulus of commercial polysiloxane sol-gel coatings.

A novel method for synthesis of polymeric nano-objects via polymerization-induced self-assembly in a CO2-expanded medium has been developed.

The successful deposition of conductive transparent TiNx/TiO2 hybrid films on both polycarbonate and silicon substrates from a titanium ethoxide precursor is demonstrated in air using atmospheric plasma processing equipped with a high‐temperature precursor delivery system. The hybrid film chemical composition, deposition rates, optical and electrical properties along with the adhesion energy to the polycarbonate substrate are investigated as a function of plasma power and plasma gas composition. The film is a hybrid of amorphous and crystalline rutile titanium oxide phases and amorphous titanium nitride that depend on the processing conditions. The visible transmittance increases from 71% to 83% with decreasing plasma power and increasing nitrogen content of the plasma gas. The film resistivity is in the range of ∼8.5 × 101 to 2.4 × 105 ohm cm. The adhesion energy to the polycarbonate substrate varies from ∼1.2 to 8.5 J/m2 with increasing plasma power and decreasing plasma gas nitrogen content. Finally, annealing the film or introducing hydrogen to the primary plasma gas significantly affects the composition and decreases thin‐film resistivity.

Hydrophilic polymer brushes based on poly(ethylene glycol) methyl ether acrylate (P(PEGA(454))) or poly(ethylene glycol) methyl ether methacrylate (P(PEGMA(475))), both having a trithiocarbonate end group, were prepared in water-dioxane (9 : 1) at 44 degrees C via RAFT polymerization, and subsequently used in RAFT dispersion polymerization of styrene in isopropanol at 90 degrees C. RAFT reaction conditions were first optimized to prepare P(PEGA(454)) and P(PEGMA(475)) macro-RAFT agents at high monomer conversions (>90%) and very low fraction of dead chains (<1%). The macro-RAFT agents were then shown to have similar efficiency in terms of reinitiating and controlling the polymerization of styrene in dispersion polymerization. Both polymer brushes allowed the preparation of well-defined amphiphilic diblock copolymers (P(PEGA(454))-b-PS and P(PEGMA(475))-b-PS) which self-assemble in situ into nano-objects with various morphologies. Using relatively long chain P(PEGA(454)) or P(PEGMA(475)) macro-RAFT agents (DP approximate to 75) leads to the formation of near uniform spherical nano-particles with diameters ranging from 30 to 140 nm, depending on the targeted DP of the PS block. In contrast, TEM and DLS studies demonstrated that using a shorter P(PEGA(454)) or P(PEGMA(475)) macro-RAFT agent (DP approximate to 20) enables the formation of worm-like micelles, vesicles and large compound vesicle morphologies, in addition to spheres. Cryo-TEM was used to confirm polymerization induced morphology transition, rather than morphologies obtained via self-assembly driven by selective solvent or solvent evaporation during the preparation of samples for characterization.

The anionic surfactant dioctyl sodium sulfosuccinate (AOT) has been shown to operate well as a surfactant in aqueous miniemulsion polymerization of styrene both for conventional radical polymerization and RAFT polymerization. AOT is generally more soluble in hydrophobic monomers than in water, and is as such rather unique for an aqueous miniemulsion system. The particle size obtained was smaller than what is customary for both conventional radical polymerization and RAFT polymerization in miniemulsion.

Polymerized ionic liquids (PILs) having guanidinium cations with different counter-anions, such as PF6- and N(CF3SO2)(2)(-) (TFSI-), were synthesized by copolymerization of a guanidinium ionic liquid monomer with methyl acrylate followed by an anion exchange reaction. Furthermore, incorporating a guanidinium ionic liquid, LiTFSI salt and nano-size SiO2, a quaternary gel polymer electrolyte based on one of the PILs as the polymer host was prepared. The quaternary gel polymer electrolyte was chemically stable even at a higher temperature of 80 degrees C in contact with the lithium anode. In particular, the electrolyte exhibited high lithium ion conductivity, wide electrochemical stability window and good lithium stripping/plating performance. Li/LiFePO4 batteries with the quaternary gel polymer electrolyte at 80 degrees C had capacities of 140 and 130 mA h g(-1) respectively at 0.1 and 0.2 C current rates. (C) 2011 Society of Chemical Industry

Mechanical degradation of the catalyst coated membrane (CCM), which contains a perfluorosulfonic acid (PFSA) proton transport layer, can significantly deteriorate the performance of proton exchange membrane (PEM) fuel cells. We initially report on the adhesive and cohesive fracture properties of CCMs and show that failure occurs cohesively in the catalyst layer (CL). We then investigate the effects of foreign cations and chloride contamination and moisture absorption on the mechanical properties of CCMs. The fracture resistance of contaminated CCMs is significantly reduced and the time dependent growth of cracks in the CLs in moist air environments occurs at lower crack driving force thresholds. The deterioration in fracture resistance of the CCMs after foreign cation contamination is related to cation interaction with the molecular structure of PFSA polymer. The harmful effect of chloride contamination is attributed to chloride blocking on the surface of catalyst Pt particles, which tends to weaken the catalyst-polymer interface and induces crack initiation and subsequent propagation with lower energy. The accelerated time dependent crack growth at higher humidity is explained by the role of water molecules on weakening ionic interactions and the intermolecular strength of the PFSA polymer.

A new kind of polymeric ionic liquid (PIL) membrane based on guanidinium ionic liquid (IL) with ester and alkyl groups was synthesized. On addition of guanidinium IL, lithium salt, and nano silica in the PIL, a gel PIL electrolyte was prepared. The chemical structure of the PIL and the properties of gel electrolytes were characterized. The ionic conductivity of the gel electrolyte was 5.07 × 10−6 and 1.92 × 10−4 S cm−1 at 30 and 80 °C, respectively. The gel electrolyte had a low glass transition temperature (T g ) under −60 °C and a high decomposition temperature of 310 °C. When the gel polymer electrolyte was used in the Li/LiFePO4 cell, the cell delivered 142 mAh g−1 after 40 cycles at the current rates of 0.1 C and 80 °C.