Monodisperse Silica‐Polymer Core‐Shell Microspheres via Surface Grafting and Emulsion Polymerization

We describe a flexible method for preparing monodisperse silica‐polystyrene core‐shell microspheres. In this method, silica nanoparticles grafted with 3‐(trimethoxysilyl)propyl methacrylate (MPS) were employed as seeds in an emulsion polymerization. The thickness of the shells could be changed through varying the amount of the monomer. The monodispersity and diameters of the core‐shell microspheres were found to depend on the size of the grafted silica nanoparticles and the concentration of emulsifier. In addition, we investigated the formation mechanism of the core‐shell microspheres.

Schematic outline of the experimental procedure and TEM image of the monodisperse silica/PS core‐shell microspheres; inset: grafted silica nanoparticles (scale bar = 200 nm).     

The Effect of Clay Loading on the Morphology and Properties of Poly(styrene‐co‐butyl acrylate)/Clay Nanocomposites

This paper investigates the effect of both the clay loading and the monomer feed rate on the morphology and properties of poly(styrene‐co‐butyl acrylate)‐clay nanocomposites prepared in emulsion polymerization. Analysis by X‐ray diffraction (XRD) and transmission electron microscopy (TEM) of the nanocomposites prepared by batch polymerization showed that the polymer clay nanocomposites (PCNs) with 1–3 wt.‐% clay loading resulted in intercalated structures, while exfoliated structures were obtained at 10 wt.‐% clay loading. The polymerization was also carried out with semi‐batch polymerization. The morphology, thermal stability, and mechanical properties of nanocomposites obtained were found to be more strongly dependent on the clay/polymer ratio than the monomer feed rate.

     

Low‐Stress Hyperbranched Polymer/Silica Nanostructures Produced by UV Curing,Sol/Gel Processing and Nanoimprint Lithography

Nanocomposite materials based on a HBP and silica are produced using either a dual‐cure sol/gel and photopolymerization process or by mixing silica nanoparticles with the HBP. In both cases the conversion of the HBP is independent of composition and obeys a time‐intensity superposition with power‐law dependence on UV intensity. Optimization of the dual‐cure process leads to transparent sol/gel composites with ultrafine structures. These materials systematically outperform the particulate composites, including an increase of the glass transition temperature of 63 °C and a process‐induced internal stress as low as 2.5 MPa. Nano‐sized gratings are produced from the sol/gel composites by low‐pressure UV nanoimprint lithography.

     

Core/Shell PBA/PMMA‐PGMA Nanoparticles to Enhance the Impact Resistance of UV‐Cured Epoxy Systems

Crosslinked core/shell PBA/PMMA‐PGMA particles are prepared by emulsion polymerization and dispersed into a UV‐curable cycloaliphatic epoxy resin in the range of 5–15 wt%. The presence of the particles does not significantly affect the UV curing process: a slight decrease of final epoxy group conversion is attributed to an increase in the viscosity when CS‐GMA is added to the photocurable formulation and to an enhanced vitrification effect. The presence of the particles does not modify the T_g of the cured materials, while an enhancement of impact resistance is observed that does not depend on the particle content. FESEM micrographs for epoxy reinforced with core/shell particles indicate a plastic void growth of the epoxy polymer and shear yielding toughening mechanism.

     

Effect of Cyclic Deformations on the Dynamic‐Mechanical Properties of Silica‐Filled Butyl Rubber

The effect of the chemical modification of the silica surface by the silane coupling agent (Si69) on both the real and the imaginary parts of the shear compliance (J′, J″) on silica‐filled butyl rubber vulcanizates was investigated in a wide temperature and frequency range, ?70 to 120 °C and 10^?4 to 10 Hz, respectively. In addition, the stress‐strain measurements, DSC, and TEM were carried out. Moreover the effect of stress‐strain cyclic deformation up to ten times with maximum deformation 80% of the elongation at break on J′, J″ is also studied. It was found that the filler network recovers after cyclic stress‐strain in a time scale of one year at room temperature.

Transmission electron photographs of the butyl rubber [IIR] vulcanizates: (a) IIR, unfilled, (b) IIR, filled with 20 phr SiO₂, (c) IIR,filled with 20 phr SiO₂ + 1.6 phr Si69.     

H‐Phosphonate‐Mediated Amination of Quinoline N‐Oxides with Tertiary Amines: A Mild and Metal‐Free Synthesis of 2‐Dialkylaminoquinolines

A synthetic strategy has been developed for the synthesis of 2‐dialkylaminoquinolines from easily available quinoline N‐oxides, tertiary amines, diisopropyl H‐phosphonate and carbon tetrachloride (CCl₄) in one pot under metal‐free conditions at room temperature.

     

Dual‐Curing of Waterborne Urethane‐Acrylate Coatings by UV and Thermal Processing

A waterbased dual‐cure urethane‐acrylate oligomer has been synthesized by polycondensation of monomers bearing hydroxyl, isocyanate and acrylate groups. To obtain a stable aqueous dispersion, carboxylate groups were grafted on the oligomer chain and the isocyanate groups were protected by a blocking agent. After water release by a brief heating, the dry films were cured either by a short UV exposure in the presence of a photoinitiator to induce the polymerization of the acrylate double bonds, or by heating up to 150 °C to release the isocyanates and promote the polycondensation by reaction with the hydroxyl groups, but mainly by a combination of UV and thermal cure. Both processes have been followed quantitatively by infrared spectroscopy to evaluate the influence of the temperature on the reaction rate and on the cure extent. The newly developed waterbased dual‐cure coatings were found to be quite resistant to accelerated weathering because of their aliphatic structure and their high crosslink density. Their light stability was substantially improved by the addition of a hydroxyphenyltriazine UV absorber and a hindered amine radical scavenger.

Thermal curing of the dual‐cure waterborne PUA formulation at a temperature of 150 °C.     

Fabrication of Amino‐Terminated Multiwalled Carbon Nanotubes via Layer‐by‐Layer Self‐Assembly Approach

MWCNT‐based composites have been successfully synthesized via layer‐by‐layer self‐assembly of crosslinked polyphosphazene nanoparticles on the surface of MWCNTs. The amino‐terminated CNTs were characterized by XPS, FT‐IR spectroscopy, EDS, XRD and TEM. The degree of functionalization could be controlled by simply changing the mass of hexachlorocyclotriphosphazene with 4,4′‐diaminodiphenyl ether. The activity of the surface amino groups was confirmed by the reaction of these groups with HAuCl₄. In addition, the effects of the mass of HCCP and ODA ratios on the content of the surface amino groups was also investigated.

     

Flexible Use of Single‐Screw Extruders through Multiple‐Process Optimization

Using general‐purpose screws to process different types of material offers considerable cost advantages over special‐purpose screws. Designing screws of this type is generally a difficult task, since modifications to different aspects of the geometry can run counter to each other in some cases. Optimization software is thus of particular benefit here. For this reason, a program was developed for the optimization of general‐purpose screws. A central feature of this program is an appraisal system for the computer‐aided evaluation of single‐screw simulations. The performance of the software was verified on the basis of actual extrusion experiments.

Temperature measuring cross for measuring thermal homogeneity.     

Infusion of SiC Nanoparticles Into SC‐15 Epoxy: An Investigation of Thermal and Mechanical Response

Summary: In the present investigation we have developed a novel technique to synthesize nanocomposite materials consisting of SC‐15 epoxy resin and silicon carbide (β‐SiC) nanoparticles. A high intensity ultrasonic liquid processor was used to obtain a homogeneous molecular mixture of epoxy resin and β‐SiC nanoparticles. In this study, we have prepared three different samples containing 0.5, 1, and 1.5% of β‐SiC nanoparticles by weight of the epoxy resin. In parallel, control samples were also made following identical procedures without the infusion of nanoparticles. Test samples were characterized by TGA, DSC and three‐point bend flexural tests to evaluate thermal and mechanical properties. The results indicate that 1 wt.‐% loading derives the maximum improvement in both thermal and mechanical properties when compared to the neat system. The dispersion of nanoparticles and morphological changes were studied by field emission scanning electron microscopy (FE‐SEM) and high resolution transmission electron microscopy (TEM). These results demonstrate that the nanoparticles are spherical in shape (≈30 nm sizes) and are uniformly dispersed over the entire volume of the resin.

FE‐SEM micrograph of the plasma etched 1 wt.‐% SiC‐epoxy system.     

Influence of Screw Speed on Electrical and Rheological Percolation of Melt‐Mixed High‐Impact Polystyrene/MWCNT Nanocomposites

The influence of screw speed on the electrical and rheological percolation of HIPS/MWCNT composites prepared via melt mixing was investigated. Microscopic examination of these composites using POM, FESEM and HRTEM revealed optimum MWCNT dispersion was achieved at intermediate screw speeds. On addition of MWCNTs to HIPS, the electrical conductivity of HIPS increased by up to 12 orders of magnitude. At screw speeds up to 100 rpm an electrical percolation of 1–3 wt.‐% was achieved. This increased to 3–5 wt.‐% when the screw speed was increased to 150 rpm. The onset of a rheological percolation was detected for an MWCNT loading of 5 wt.‐%, irrespective of screw speed employed. An up‐shift in the Raman G‐band of 24 cm^?1 was observed, implying strong interfacial interaction between HIPS and MWCNTs.

     

UV‐Cured Acrylic Conductive Inks for Microelectronic Devices

UV‐curable inks based on a poly(ethylene glycol) diacrylate (PEGDA) matrix and containing a dispersion of aqueous Ag nanoparticles in different amounts from 10 to 50% are prepared for the fabrication of inkjet printed resistors. The composition is adapted to the inkjet requirements in terms of viscosity, surface tension, and particle size. The gel content, glass transition temperature, conversion, UV‐Vis absorption, morphology, and DC electrical properties of the materials are characterized. It is found that the NPs dispersed in the polymeric matrix realize a percolating path by aligning themselves in chains, which results in a reduction of the percolation threshold. Thus, resistivity is well beyond the dissipative range.

     

UV‐Induced Cross‐Linking of Poly(ethylene oxide) in Aqueous Solution

Summary: Hydrogels of high‐molecular‐weight poly(ethylene oxide) (PEO) have been obtained in situ by applying a very simple procedure that involves UV cross‐linking of PEO in aqueous solution. The efficiency of the photoactivated cross‐linking of thin layers of PEO in aqueous solution in the presence of (4‐benzoylbenzyl) trimethylammonium chloride as a photoinitiator has been determined at room temperature and in a frozen state (?25 °C). It was found that the efficiency varies with the concentration of PEO solution, the molecular weight of PEO, and especially with the temperature. When the UV cross‐linking was performed in the frozen state, porous hydrogels with very high yield of gel fraction (above 90%) and high cross‐linking density were obtained. After drying the hydrogels, films of 50–150 μm thickness were prepared. The films swell extremely fast in water and act as asymmetric membranes.

SEM of a dried PEO hydrogel obtained by UV cross‐linking of an aqueous solution at room temperature.     

In Situ Preparation of a Compatibilized Poly(cis‐1,4‐butadiene)/Poly(ε‐caprolactone) Blend

The ternary Ziegler‐Natta‐type catalyst system based on neodymium versatate (NdV), diisobutylaluminium hydride (DIBAH) and ethylaluminium sesquichloride (EASC) was used for the in situ preparation of a compatibilized blend consisting of poly(cis‐1,4‐butadiene) (BR = butadiene rubber) and poly(ε‐caprolactone) (PCL). Poly(cis‐1,4‐butadiene)‐block‐poly(ε‐caprolactone) which acts as compatibilizer for the two immiscible polymers BR and PCL was obtained by a two step sequential polymerization with the preparation of a living cis‐1,4‐BR building block in the first stage and the subsequent polymerization of CL during the second stage. This preparation method resulted in a polymer blend comprising the homopolymers BR and PCL as well as the block copolymer BR‐block‐PCL. For detailed characterization the block copolymer was separated from the respective homopolymers BR and PCL by means of fractionation with the binary solvent mixture dimethylformamide/methylcyclohexane (DMF/MCH) which mixes well at elevated temperature and exhibits phase separation at ambient temperature. ¹H NMR, IR, SEC and TEM were used for characterization of the block copolymer.

TEM of BR‐block‐PCL.     

Blends of a Main Chain Liquid‐Crystalline Polyester with a Diepoxide and with a Diepoxide/Amine Mixture Prepared in a Twin‐Screw Extruder

Summary: Blending of the commercial LC‐polyester Rodrun LC‐3000 with the bisphenol‐A‐diglycidyl ether based diepoxide DOW D.E.R.330 alone and with the mixture of the diamine (MCDEA) and D.E.R.330 by means of a twin‐screw extruder has been investigated. Conditions to suppress curing of epoxide and amine during blending have been established. Due to the very low solubility of Rodrun in the diepoxide only LCP‐rich blends with a minimum content of 60 wt.‐% Rodrun could be obtained. The blends were investigated by SEM and thermal analysis (DSC, DMTA). Binary blends are immiscible while ternary blends appear miscible from DMTA up to 30 wt.‐% of epoxy/amine.

SEM micrograph of Rodrun moulded at 230 °C.     

Bio‐Based Nanocomposites from Corn Oil and Functionalized Organoclay Prepared by Cationic Polymerization

A reactive organic montmorillonite clay (VMMT), modified with (4‐vinylbenzyl) triethylammonium cations, has been prepared and used as a nanofiller to reinforce a corn‐oil‐based polymer resin. The polymer resin was prepared by the cationic polymerization of conjugated corn oil, styrene and divinylbenzene, using boron trifluoride diethyl etherate modified with Norway fish oil as the initiator. The results indicate that the VMMT is intercalated in the corn‐oil‐based polymer resins. When compared with the pure polymers, these novel nanocomposites reinforced with 2 to 3 wt.‐% VMMT exhibit significant improvements in modulus, strength, strain and toughness. Furthermore, incorporating VMMT into the corn‐oil‐based polymer matrix also leads to improved thermal stability of the nanocomposites over the pure resins of up to 400 °C.

     

An Application of Silica‐Based Monolithic Membrane Emulsification Technique for Easy and Efficient Preparation of Uniformly Sized Polymer Particles

Summary: Uniformly sized polymer particles were prepared by an emulsification and polymerization technique utilizing a silica monolithic membrane, namely the “silica monolithic membrane emulsification technique”. In this paper, we utilized silica monolithic membrane as a device for the preparation of uniformly sized polymer particles. A mixture of monomers, diluents and oil‐soluble initiator was emulsified into a continuous medium through the silica monolithic membrane and polymerized. The particles obtained had a higher size uniformity than that of particles prepared by previously reported membrane emulsification techniques, such as the Shirasu Porous Glass (SPG) emulsification technique. Through the silica monolithic membrane emulsification technique, we could prepare particles having availability as a possible packing material for solid‐phase extraction (SPE) and high performance liquid chromatography (HPLC).

SEM photograph of silica particles prepared through capillary plate membrane.     

Cationic UV‐Curable Conductive Composites from Exfoliated Graphite

Electrically conductive, cationically UV‐cured composites were prepared using exfoliated graphite plates (EGP) with cycloaliphatic epoxy resin and polyalcohol binder system. Exfoliated graphite (EG) was obtained from natural flake graphite through chemical and thermal treatment. Sonication of EG in solvent produced EGP. Characterization of graphite samples by XRD showed structural similarity between original graphite and EGP. UV curing behavior was characterized using photoDSC. Electrical resistivity measurements of the composites as a function of EGP concentration showed that at low filler concentration the binder system can influence the electrical percolation behavior. Some formulations showed electrical percolation at less than 1 vol.‐% of EGP filler.

     

Effect of Silica‐Coated Poly(butyl methacrylate)‐block‐poly(methyl methacrylate) Double‐Shell Particles on the Mechanical Properties of PMMA Composites

Silica nanoparticles with an average diameter of 12 nm are grafted with PBMA‐b‐PMMA double shells through typical sequential ATRP from bromoisobutyrate initiators anchored at the silica surface using an epoxysilane. A commercially available PMMA homopolymer is used for the preparation of composites with unmodified, silane‐modified and double‐shell‐modified silica particles. Good mechanical properties are obtained for silica double shell containing systems. The silica content in double shell particle systems is varied from 0 to 2.5 wt%. A significant improvement in impact properties is observed. The surface‐modified silica particles are characterized by ATR‐FTIR, NMR, GPC, and thermal analyses. TEM analysis is used to analyze the nature of dispersion of particles in the composites.

     

Influence of Stabilizer Concentration on Transport Behavior and Thermopower of CNT‐Filled Latex‐Based Composites

The influence of the stabilizer/SWNT ratio on the transport behavior of latex‐based polymer nanocomposites is examined in an effort to improve electrical conductivity while maintaining or improving the Seebeck coefficient (i.e., thermopower). Results show that phonon and electron transport are significantly affected by tube/tube junctions, and the carrier transport across the junctions can be manipulated by altering the stabilizer concentration. Electrical conductivity of composites containing 10 wt.‐% SWNT nearly doubles, becoming greater than 900 S · m^?1, by changing the SWNT:GA ratio from 1:3 to 10:1, while thermal conductivity and Seebeck coefficient remain relatively constant (near 0.25 W · m‐K^?1 and 40 µV · K^?1, respectively).