Cationic nanogels based on diethylaminoethyl methacrylate

The effect of polymer composition and polymerization parameters such as comonomers, crosslinking ratio, and polymerization method, on the surface characteristics, surface chemistry, and swelling response of crosslinked 2-(diethylaminoethyl methacrylate) (DEAEM) and polyethylene glycol monoethyl ether monomethacrylate (PEGMMA) nanogels was studied. A novel inverse emulsion polymerization method was developed, which formed latex nanoparticles on the order of 100-400 nm. The properties of these nanogels were compared to microparticles synthesized via solution polymerization. The new polymerization method allowed the incorporation of PEG surface tethers of lengths 400 Da up to 2000 Da. Surface tethers successfully decreased the ζ-potential of these nanogels from 70 mV to 30 mV in acidic conditions and from −60 mV to 2 mV in basic media. Nanogels swelled from 100 nm in basic media to 800 nm in acidic media due to the protonation of the tertiary amine on DEAEM.     

Thermoset–thermoplastic hybrid nanoparticles and composite coatings

Structured thermoset–thermoplastic hybrid nanoparticles and composite coatings were successfully synthesized through a novel one-pot approach. Both the polyaddition of epoxy curing and the free radical polymerization of various vinyl monomers were performed in sequence in miniemulsion droplets. Benefiting from the precise control of the compatibility between thermoset phase (epoxy monomer/amine curing agent) and vinyl phase (vinyl monomers/polymers), colloidally stable, core–shell structured thermoset–thermoplastic hybrid nanoparticles between 100 and 200 nm were obtained through chemically induced phase separation. The influence of the compositions on the colloidal stability and morphology of the final hybrid latexes and films was studied in detail. Meanwhile, the mechanical properties of thermoset–thermoplastic coatings and corresponding thermoplastic coatings were investigated. It is found that the thermoset–thermoplastic composite coatings showed significantly improved film properties in terms of hardness compared to the analogous thermoplastic coatings. Furthermore the thermoset–thermoplastic hybrid films were highly transparent even with 33 wt% of epoxy thermoset domains embedded.     

Photoinitiators based on a phenazine scaffold: High performance systems upon near-UV or visible LED (385, 395 and 405 nm) irradiations

Novel photoinitiators based on a phenazine scaffold are proposed for the ring opening polymerization of epoxy monomers as well as the free radical polymerization of (meth)acrylates. Good to excellent polymerization profiles can be obtained upon different easily accessible, energy saving and cheap LEDs (385, 395 and 405 nm) as well as a diode laser at 405 nm or halogen lamp opening new fields for polymer synthesis upon soft and convenient irradiations. These compounds can be particularly attractive as high performance photoinitiators in the 350–425 nm range. The initiation mechanisms are investigated in detail through fluorescence, cyclic voltammetry, steady state photolysis and electron spin resonance (ESR) experiments.     

Preparation and comparative evaluation of well-defined fluorinated acrylic copolymer latex and solution for ancient stone protection

In this work the well-defined fluorinated acrylic copolymer latex and solution were prepared by the radical initiated seed emulsion polymerization and solution polymerization, respectively, using the same monomers of dodecafluoroheptyl methacrylate (DFHM), butyl acrylate (BA) and methyl methylacrylate (MMA). The copolymer latex BA/MMA/DFHM was designed as core–shell structure and the copolymer solution poly(BA–MMA–DFHM) was structured with low molecular weight. The chemical and morphology structures as well as the film properties obtained from latex and solution were analyzed and compared by spectroscopic techniques (FT-IR and NMR), transmission electron microscopy (TEM), differential scanning calorimetry (DSC), gel permeation chromatography (GPC), scanning electron microscopy coupled with energy-dispersive X-ray detector (SEM–EDX) and static contact angles (CAs) instrument. Moreover, the BA/MMA/DFHM latex and poly(BA–MMA–DFHM) solution (with 29 wt% of DFHM) were applied onto two kinds of sandstone samples by capillary absorption, and their preliminary protecting efficiency was evaluated. It is demonstrated that the comprehensive performances of BA/MMA/DFHM latex films were quite comparable to those of poly(BA–MMA–DFHM) solution cast films, the latter exhibited a better protective performance.     

Effect of annealing process on the growth and surface properties of Au–ZnO nanowire films grown by chemical routes

Au–ZnO nanowire films have been synthesized by chemical routes, electrochemical deposition (ECD) and chemical bath deposition (CBD) techniques, on zinc foil followed by annealing in air at 400 °C. X-ray diffraction patterns reveal formation of the ZnO wurtzite structure along with binary phases Au₃Zn and AuZn₃. Scanning electron microscopy shows the presence of ZnO nanowires having several micrometers in length and less than 120 nm in diameter synthesized by ECD and in the range of 70–400 nm using the CBD technique. During the annealing process, different surface morphologies originating from different catalytic effects of Au atoms/layers were observed. In addition, the effect of synthesis routes on crystalline quality and optical properties were studied by Raman and photoluminescence spectrometers indicating varying concentration of defects on the films. The Raman results indicate that Au–ZnO nanowire film prepared by chemical bath deposition route had better crystalline quality.     

ZnO nanosphere fabrication using the functionalized polystyrene nanoparticles for dye-sensitized solar cells

The nano-hollow spherical ZnO (NHS ZnO) photoelectrodes were prepared using functionalized polystyrene nanoparticles with flexible dimensional control of the particle diameter for dye-sensitized solar cells applications. NHS ZnO was formed by ZnO nanoparticles that accumulated on the surface of functionalized polystyrene with a high ionic strength. This method represents a one-step preparation method for an inorganic shell via polymerization between ZnO complexes. Even though NHS ZnO has a submicron size, it composed of nanoparticles that connect with each other, thereby implying good electron transfer properties, and has a high surface area. The submicron-sized diameter NHS ZnO has an enhanced light scattering capacity, which promotes the photons with more opportunities to be absorbed by the N719 dye molecules. Therefore, the ZnO films prepared from 600 nm to 1000 nm NHS ZnO possessed higher IPCE values over a wide range (from 400 nm to 750 nm) compared to films of the 300 nm ZnO due to the enhanced light scattering capacities of the film. In photocurrent-voltage measurements, the short-circuit current density of 300 nm and 600 nm NHS ZnO increases from 3.33 mA/cm² to 6.53 mA/cm² while the cell efficiency increases from 1.04% to 3.02% due to the light scattering efficiency. Electrochemical impedance spectroscopy showed that electrons in NHS ZnO with a larger particle size have a longer electron lifetime than NHS ZnO with a smaller particle size, as the latter hinders the electron transport in the NHS ZnO nanostructured films.     

Modulation of Fluorescence of a Terbium-Complex-Containing Polymer by Gold Nanoparticles through Energy Transfer

A terbium complex-containing polymer (P-Tb) is prepared via free radical polymerization in solution. The copolymer exhibits the characteristic fluorescence bands of Tb³⁺ complex as well as a strong and broad band at near 400 nm. The fluorescence of P-Tb can be modulated by gold nanoparticles, with the gradual addition of gold nanoparticles into the DMF/toluene solution of P-Tb. The intensity of the characteristic emissions steadily decreases whereas the broad band at ca. 400 nm experiences fluorescence enhancement. For the solid films of P-Tb with varied amount of gold nanoparticles, both the characteristic emissions and the broad band suffers fluorescence quenching. The absorption of gold nanoparticle solution exhibits a prominent red-shift upon addition of P-Tb, suggesting there exists strong binding between the Tb/β-diketone complexes and gold nanoparticles. It is thought that the energy transfer is the driving force for the change in fluorescence intensity; and, the difference in polymer chain conformation in solution and in the solid state leads to different fluorescence behaviors for solution and solid samples.     

Performance enhancement of dye-sensitized solar cells using nanostructural TiO2 films prepared by a graft polymerization and sol–gel process

Nanostructural TiO₂ films with large surface areas were prepared by the combined process of graft polymerization and sol–gel for use in dye-sensitized solar cells (DSSCs). The surface of the TiO₂ nanoparticles was first graft polymerized with photodegradable poly(methyl methacrylate) (PMMA) via atom transfer radical polymerization (ATRP), after which the particles were deposited onto a conducting glass. The PMMA chains were removed from the TiO₂ films by UV irradiation to generate secondary pores, into which titanium isopropoxide (TTIP) was infiltrated. The TTIP was then converted into small TiO₂ particles by calcination at 450 °C, as characterized by energy-filtering transmission electron microscopy (EF-TEM) and field emission scanning electron microscopy (FE-SEM). The nanostructural TiO₂ films were used as a photoelectrode in solid-state DSSCs; the energy conversion efficiency was 5.1% at 100 mW/cm², which was higher than the values achieved by the pristine TiO₂ (3.8%) and nongrafted TiO₂/TTIP photoelectrodes (3.3%). This performance enhancement is primarily due to the increased surface area and pore volume of TiO₂ films, as revealed by the N₂ adsorption–desorption isotherm.     

Polymerization behavior and polymer properties of eosin-mediated surface modification reactions

Surface modification by surface-mediated polymerization necessitates control of the grafted polymer film thicknesses to achieve the desired property changes. Here, a microarray format is used to assess a range of reaction conditions and formulations rapidly in regards to the film thicknesses achieved and the polymerization behavior. Monomer formulations initiated by eosin conjugates with varying concentrations of poly(ethylene glycol) diacrylate (PEGDA), N-methyldiethanolamine (MDEA), and 1-vinyl-2-pyrrolidone (VP) were evaluated. Acrylamide with MDEA or ascorbic acid as a coinitiator was also investigated. The best formulation was found to be 40 wt% acrylamide with MDEA which yielded four to eightfold thicker films (maximum polymer thickness increased from 180 nm to 1420 nm) and generated visible films from fivefold lower eosin surface densities (2.8 versus 14 eosins/μm²) compared to a corresponding PEGDA formulation. Using a microarray format to assess multiple initiator surface densities enabled facile identification of a monomer formulation that yields the desired polymer properties and polymerization behavior across the requisite range of initiator surface densities.     

Organosoluble semi-alicyclic polyimides derived from 3,4-dicarboxy-1,2,3,4-tetrahydro-6-tert-butyl-1-naphthalene succinic dianhydride and aromatic diamines: Synthesis,characterization and thermal degradation investigation

Semi-alicyclic polyimides (PI-1–PI-4) have been prepared from a newly-developed alicyclic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-6-tert-butyl-1-naphthalene succinic dianhydride (TTDA) and various aromatic diamines. The asymmetrical alicyclic tetralin structure in TTDA endowed the derived PI resins good solubility in various organic solvents. They were soluble not only in polar aprotic solvents but also in solvents with low boiling points including dichloromethane and tetrahydrofuran. Flexible and tough PI films were successfully cast from their N-methyl-2-pyrrolidone (NMP) solution except PI-1 derived from TTDA and 4,4′-oxydianiline (ODA). The PI films exhibited good optical transparency in the ultraviolet and visible light region with optical transmittances around 80% at a wavelength of 400 nm. The PI films showed good thermal stability up to 400 °C in nitrogen, after that they thermally decomposed rapidly. The thermal degradation behaviors of the PIs were investigated by means of thermogravimetric analysis-mass spectrometry (TG-MS), thermogravimetric analysis-Fourier transform infrared spectrometry (TG-FTIR) and the real time FTIR spectra (RT-FTIR) analysis techniques. The results revealed that the decomposition of PI-1 (as a representative) took place mainly in the range of 450–550 °C. The major degradative fragments at 500 °C were clearly identified as the tert-butyl-substituted tetralin moiety and its dealkylation products. Therefore, it can be deduced that for the TTDA-PIs, the single bond bridge attached the maleic anhydride and tetralin anhydride units in TTDA moiety might break first during the heating; thus producing the tetralin fragments.     

Phase evolution and electrical properties of lead zirconate titanate thin films grown by using a triol sol–gel route

Lead zirconate titanate (PZT) precursor sols were prepared using a triol based sol–gel route. Inorganics salts metal alkoxides lead acetate trihydrate [Pb(OOCCH₃)₂·3H₂O], titanium (IV) isopropoxide [Ti(OCH(CH₃)₂)₄], and zirconium n-propoxide [ZrOC₃H7)₄] were used as starting materials. Thin films were deposited by spin coating onto Pt/Ti/SiO₂/Si substrates. The samples were pre-heated (pyrolysis) on a calibrated hotplate over the temperature range of 200–400 °C for 10 min then firing at a temperature of 600 °C for 30 min. Randomly-oriented PZT thin films pre-heated at 400 °C for 10 min and annealed at 600 °C for 30 min showed well-defined ferroelectric hysteresis loops with a remanent polarization of 27 μC/cm² and a coercive field of 115 kV/cm. The dielectric constant and dielectric loss of the PZT films were 621 and 0.040, respectively. The microstructures of the thin films are dense, crack-free and homogeneous with fine grains about 15–20 nm in size.     

Nanostructured MoSx-based thin films obtained by electrochemical reduction

The in situ electrochemical deposition of nanostructured MoS_x (x = 1.5–1.7) based thin films on various substrates from aqueous solutions is reported. The as-deposited amorphous films transform on annealing into crystalline ones as revealed by a stepwise high temperature X-ray diffraction (XRD). Both Raman spectroscopy and XRD crystal structure analyses confirmed the formation of inorganic fullerene-MoS_x nanoparticles (IF-MoS_x). The as-deposited thin films have a featureless surface morphology, but after annealing either a nanotube or a nanorod structure along with numerous smaller nanoballs appear at the surface. An investigation by transmission electron microscopy unearths the presence of nanoballs, nanoribbons, and nanotubes throughout the annealed MoS_x thin films. The size of the nanoballs is in the range of 5–10 nm. The nanotubes have a diameter of 10–400 nm, and a length of up to several micrometers as evidenced by SEM. The catalytic effect of transition metals on the growth of nanotubes is noticed. The temperature-induced transformation from amorphous to crystalline structured MoS_x films results in a large lowering of the coefficient of friction under sliding against corundum in ambient air of 50% relative humidity.     

Synthesis of star polymers by “core-first” one–pot method via ATRP: Monte Carlo simulations

Results of the simulation of star polymers synthesis by one–pot, core–first method are presented. The simulated ideal living polymerization process consists of two steps. In the first one (core growth) an atom transfer radical polymerization (ATRP) of a crosslinker is performed. When the crosslinker conversion is close to completion, a bifunctional monomer is added and the ATRP polymerization of the monomer takes place from the obtained cores to form linear arms of the stars. The simulation method is based on dynamic lattice liquid (DLL) algorithm, which takes into account changes of local dynamics resulting from polymerization and formation of complex polymer molecules. In the first stage of the synthesis (core formation), in addition to the effect of concentrations of initiator and crosslinker, the rate of intramolecular crosslinking is also very important. This process “consumes” the reactive crosslinker in the cores, limiting the core size and preventing further star–star coupling. The effect of various parameters on star size and internal structure was studied. These parameters involve the rate of intramolecular crosslinking, initial concentrations of the components and the moment of monomer addition. The results can be used as guidelines for the experimental work on star synthesis.     

Formation of mesoglobules in aqueous media from thermo-sensitive poly(ethoxytriethyleneglycol acrylate)

A series of six poly(ethoxytriethyleneglycol acrylate) (PETEGA) homopolymers were synthesized by atom transfer radical polymerization, reversible addition-fragmentation transfer polymerization, and anionic polymerization in order to cover a molecular weight range from 7,000 to 40,000 Da. The polymers exhibited a lower critical solution temperature (LCST) behavior in water, which was observed by the occurrence of a cloud point (CP) at around 35 °C. The transmittance of visible light versus temperature dependence overlapped during the cooling and the heating cycles, showing almost a complete lack of hysteresis. Moreover, instead of the occurrence of an uncontrolled macroscopic phase separation, stable colloidal aggregates (mesoglobules) of narrow distribution in particle size were formed in water at temperatures above the LCST of PETEGA at 1 g L⁻¹ solutions. The dimensions of the mesoglobules ranged from 91 to 235 nm, and particle size was not influenced by the molecular weight of PETEGA. Temperature changes caused considerable variations of the mesoglobules dimensions, which were smaller at higher temperatures. The addition of an anionic surfactant simultaneously increased the CP values by 4–6 °C and lowered the dimensions of the mesoglobules.     

Synthesis and characterization of electroactive films based on benzo(a)pyrene

The polycyclic aromatic hydrocarbons (PAHs) are a group of compounds that might have practical applications due to their graphene-like properties. Derivatized PAHs can self-assemble in liquid crystal form. The chemical synthesis of large size PAHs can however be complicated and problematic. Electrochemical synthesis of PAHs molecules was studied in this work by cyclic voltammetry. Benzo(a)pyrene was used as the monomer. The resulting electroactive films consist of different PAHs in both size and symmetry. We call this mixture poly(benzopyrene) (PBP). The synthesis conditions of PBP were optimized to obtain thick and electrochemically stable films. The best film quality was achieved by potential scanning in propylene carbonate at low scan rate resulting in continues polymer growth during 10 scans giving approx. a 1 μm thick PBP film. During p- and n-doping studies the reduction and oxidation peaks were observed at 1.0 V and −1.6 V, respectively, with an electrochemical band gap of approx. 2.6 eV. The in situ UV–vis characterization of the PBP films was made by applying a constant potential with increasing steps. The optical band gap was approx. 2.5 eV and the absorption maximum was observed at ca. 420 nm. During p- and n-doping new induced bands were formed in the range 575–600 nm. UV–vis spectroscopy indicate that PBP mainly consist of units consisting of more than 40 carbon atoms and large number of π-electrons.     

Preparation and characterization of stable and high solid content St/BA emulsifier-free latexes in the presence of AMPS

Stable and high solid content (about 50 wt%) St/BA emulsifier-free latexes were successfully synthesized using emulsifier-free emulsion polymerization with the addition of a small amount of reactive emulsifier AMPS. Properties of the latexes, such as the average particle diameter and its distribution, the morphology of latex particles, and stability were investigated. Physical properties of the latex films, i.e., glass transition temperature (T _g), water resistance, and solvent resistance were investigated as well. The size of latex particles is 400–600 nm in diameter, which is larger than that prepared by conventional emulsion polymerization. And the particle size distribution is narrow and uniform. It was found that the diameter of the latex particles decreases with the increasing content of the initiator KPS and the reactive emulsifier AMPS. Compared with the film prepared by conventional emulsion polymerization, water resistant and solvent resistant of the films prepared by emulsifier-free emulsion polymerization are improved greatly.     

Growth mechanism of transparent and conducting composite films of polyaniline

Composites of polyaniline (PANI) with various polymeric matrices as substrates were synthesized by means of diffusion–oxidation of aniline swollen polymeric matrices with FeCl₃ as oxidizer. The conductivity at room temperature, transmittance at 400–800 nm, stability in air, and morphology of PANI composite films depend on the polymerization time, concentration of FeCl₃, and substrate used. A maximum conductivity at room temperature and the highest transmittance at 500–800 nm can be achieved of 10^?1 S/cm and 70–80%, respectively. The growth mechanism of PANI composite films has been discussed. © 1993 John Wiley & Sons, Inc.     

Novel addition-fragmentation agent in cationic photopolymerization

The aim of present study is to examine the photo-initiation efficiency of N,N-dimethylacrylamide-based allylic ammonium salt as one component addition-fragmentation agent (cationic photoinitiator cum radical source) in free radical accelerated cationic polymerization. Novel addition-fragmentation agent (AFA), 2-(N,N-dimethylcarboxy-3-propenyl)(phenylcarbonyl-4-phenylene) dimethyl ammonium hexafluoroantimonate (DMPDA) was synthesized as cationic photoinitiator and its initiation efficiency was examined in polymerization of cyclohexene oxide (CHO), isobutyl vinyl ether (IBVE), and n-butyl vinyl ether (n-BVE) in CH₂Cl₂ solvent at wavelength λ > 290 nm. The rate of polymerization increases with the increase in initiator concentration and reaction time. The results demonstrate that DMPDA acts as an efficient photoinitiator (AFA) without use of radical source in free radical accelerated cationic polymerization.     

Nano-scale core–shell structural casein based coating latex: Synthesis,characterization and its biodegradability

Nano-scale core–shell type particle of caprolactam-butylacrylate co-modified casein (CA-CPL-BA) bearing poly(butylacrylate) core and casein-caprolactam shell was synthesized via emulsifier-free polymerization, and was applied as the film-former in leather finishing. By utilizing potassium persulfate–sodium hydrogensulfite as a redox pair during preparing CA-CPL-BA, the grafting extent was superior to that initiated by ammonium persulfate–sodium hydrogensulfite, potassium persulfate or ammonium persulfate. Transmission electron microscopy (TEM) and dynamic light scattering (DLS) analysis results demonstrated that the average size of neat casein particle was around 700 nm while the resultant CA-CPL-BA latex particles were significantly decreased to about 80 nm in size. Compared with those of neat casein films, enhanced hydrophobicity and higher thermo-stability of the CA-CPL-BA latex film were confirmed by contact angle test and thermal gravimetric (TG) measurement, respectively. Meanwhile, the application performance of the leather samples finished by CA-CPL-BA was proved to be equivalent to that finished by the commercial leather finishing agent product. A possible mechanism of emulsifier-free polymerization for this system was proposed and then proved. Biodegradability tested by soil burial degradation experiments proved that CA-CPL-BA had preferable biodegradability.     

Sol–gel-deposition of thin TiO2:Eu thermographic phosphor films

A relatively new promising method for surface temperature measurement is the use of thermographic phosphors. For this application, the temperature-dependent luminescence properties of europium (III)-doped anatase (TiO₂:Eu³⁺) thin films were studied. The films were prepared by the sol–gel method using dip coating. The structures and the morphology of the films were determined by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. Electron dispersive X-ray spectroscopy (EDX) was used to verify the europium concentration within the films. For using the films as temperature sensors the optical properties are the main concern. Therefore, the emission spectra of the films were measured after ultraviolet laser excitation (355 nm). They indicate that the red characteristic emission (617 nm) of TiO₂:Eu³⁺ due to the ⁵D₀ → ⁷F₂ electric dipole transition is the strongest. The decay time constant of the exponential emission decay under UV excitation with a Nd:YAG laser (355 nm, f = 10 Hz) is strongly temperature dependent in the range from 200 °C up to 400 °C; making it useful for temperature evaluation. The temperature dependence was measured for the emission line at 617 nm; the results demonstrate that anatase doped europium (III) can be used as a thermographic phosphor.