Preparation,characterization and dielectric properties of polyetherimide nanocomposites containing surface‐functionalized BaTiO3 nanoparticles

Polyetherimide (PEI)/hydroxyl‐functionalized barium titanate (BaTiO₃) nanocomposite films were successfully prepared through solution‐casting followed by subsequent thermal imidization. The results of Fourier transform infrared spectroscopy confirmed that the chemical treatment with hydrogen peroxide (H₂O₂) could efficiently derive hydroxyl groups on the surface of BaTiO₃ nanoparticles. The strong interaction between the hydroxyl‐functionalized BaTiO₃ and the PEI matrix greatly enhanced the particle dispersion as well as the interfacial adhesion, as evidenced by scanning electron microscopy. The PEI nanocomposite with hydroxyl‐functionalized BaTiO₃ nanoparticles (50 vol% BaTiO₃ loading) showed an increased dielectric permittivity of 52.78 at 1 kHz compared with the dielectric permittivity (33.87) of PEI/raw BaTiO₃ composite. The loss tangent was still low (less than 0.03) when the content of hydroxyl‐functionalized BaTiO₃ was 50 vol%. For PEI/BaTiO₃ nanocomposites, the frequency and temperature dependences of the dielectric properties were significantly reduced through functionalizing the surface of BaTiO₃ nanoparticles with H₂O₂. Different theoretical approaches were employed to predict the effective permittivity of the nanocomposite systems and the results are compared with the experimental results. Copyright © 2012 Society of Chemical Industry     

Molecularly imprinted polymer nanomaterials and nanocomposites by controlled/living radical polymerization

Since the pioneering work of Wulff and Mosbach more than 30 years ago, molecular imprinting of synthetic polymers has emerged as a robust and convenient way for synthesizing polymeric receptor materials bearing specific recognition sites for target molecules. The resulting materials, molecularly imprinted polymers (MIPs), are therefore commonly referred to as ‘plastic antibodies’. They are obtained by polymerizing a scaffold around a target, or a derivate thereof, which acts as a molecular template. MIPs have been successfully applied in many areas including affinity separation, immunoassays, chemical sensing, solid-phase extraction, drug delivery, cell and tissue imaging, direct synthesis and catalysis. In terms of affinity and selectivity, MIPs are on a par with biological receptors like antibodies, and this is accompanied by a superior chemical and physical stability, compatibility with organic media, reusability, easy engineering and low cost. These advantages represent the main reasons for the wide interest raised around molecularly imprinted materials. Mainly produced by free radical polymerization (FRP) of vinyl monomers, MIPs have also taken advantage of the introduction of controlled/living radical polymerization (CRP) techniques, which have literally transformed polymer chemistry over the last decade. This review describes the advantages arising from the use of CRP in synthesizing MIPs, both in terms of sheer binding properties as well as for their remarkable potential for post-polymerization functionalization, for the synthesis of MIP nanomaterials and for the integration of MIPs into composites and hybrid materials. The benefits of using CRP are critically assessed with respect to the still largely applied FRP and guidelines are provided for choosing the most convenient technique to fit a specific targeted application of MIPs.     

Gold nanoparticle-mediated fluorescence enhancement by two-photon polymerized 3D microstructures

Fluorescence enhancement achieved by functionalized microstructures made by two-photon polymerization (TPP) is reported for the first time. Microstructures of various shapes made of SU-8 photoresist were prepared and coated with gold nanoparticles (NP) of 80 nm. Localized fluorescence enhancement was demonstrated by microstructures equipped with tips of sub-micron dimensions. The enhancement was realized by positioning the NP-coated structures over fluorescent protein layers. Two fluorophores with their absorption in the red and in the green region of the VIS spectrum were used. Laser scanning confocal microscopy was used to quantify the enhancement. The enhancement factor was as high as 6 in areas of several square-micrometers and more than 3 in the case of local enhancement, comparable with literature values for similar nanoparticles. The structured pattern of the observed fluorescence intensity indicates a classic enhancement mechanism realized by standing waves over reflecting surfaces. With further development mobile microtools made by TPP and functionalized by metal NPs can be actuated by optical tweezers and position to any fluorescent micro-object, such as single cells to realize localized, targeted fluorescence enhancement.     

Diazonium functionalization of graphene nanosheets and impact response of aniline modified graphene/bismaleimide nanocomposites

For developing high performance of graphene-based nanocomposites, dispersibility of graphene sheets in matrices and interfacial interaction are challenging due to the strong tendency of agglomeration and surface inertia of graphene. Here we report an efficient way to functionalize graphene nanosheets with aniline groups on their surfaces, to attain the functionalized graphene nanosheets (FGS) by diazonium treatment following reduction of graphene oxide with hydrazine hydrate. Two kinds of nanocomposites based on diallyl bisphenol A modified bismaleimide (BMI-BA) resin which was filled with functionalized graphene and reduced graphene oxide nanosheets were prepared, and the FGS were linked with BMI resin by chemical bonds. The FGS/BMI-BA composite at a loading of 0.3 wt% revealed a 39% increase in impact strength and a slightly improvement in flexural strength, and the resulting composite remains stable at high temperature. This work provides more possibilities for incorporation of graphene into polymer matrices and an efficient method to toughening the BMI resin.     

Atom transfer radical polymerization of glycidyl methacrylate followed by amination on the surface of monodispersed highly crosslinked polymer microspheres and the study of cation adsorption

The introduction of reactive groups on the surface of monodispersed highly crosslinked poly(styrene–divinylbenzene) (PSDVB) microspheres was accomplished in two steps. The first step requires immobilizing the initiating groups by a Friedel–Craft acylation between 2-chloropropionyl chlorides and the phenyl groups on the spheres. The second step requires the atom transfer radical polymerization (ATRP) of glycidyl methacrylate (GMA) to obtain spheres (PSDVB-g-PGMA) with epoxy groups on the surface. To demonstrate the feasibility of introducing functionality, the epoxy groups were ring-opened by ethylenediamines, resulting in spheres with amino functionality (PSDVB-g-PGMAEDA). The final spheres were found to have an adsorption capacity of 0.66 mmol/g in the Cu²⁺ adsorption experiments, as a preliminary application study.     

Additional doping of phosphorus into polypyrrole functionalized nitrogenous carbon nanotubes as novel metal-free oxygen reduction electrocatalyst in alkaline solution

Novel phosphorus-doped polypyrrole functionalized nitrogenous carbon nanotubes (P/NCNTs) was developed for the first time as metal-free electrocatalyst for enhancing the oxygen reduction reaction (ORR) activity in alkaline medium. The P/NCNTs was successfully synthesized by pyrolyzing PPy and triphenylphosphane (TPP) under N₂, using pyrrole as carbon and nitrogen precursors, TPP as phosphorus precursor. Various characterizations such as transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman spectra, Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) reveal that the P/NCNTs material has covalently bound P atoms with carbon framework, which can introduce defect sites and can induce uneven charge distribution. Moreover, the content of pyridine N increased after P-doping, which is of great significance in improving the ORR activity. The electrochemical behavior of the resultant material shows that the P/NCNTs has much enhanced electroactivity and better stability for ORR. Additionally, a direct four-electron pathway occurred efficiently on P/NCNTs modified electrode. These enhanced performances indicate that P/NCNTs catalyst may be an excellent cathode catalyst for ORR.     

Functionalization of Polymer Surfaces Using Excimer VUV Systems and Silent Discharges. Application to Electroless Metallization

New approaches for electroless plating of nonconductive polymers or polymer-based materials are described. In this work, polyimide substrates were surface-functionalized (i) in nitrogenated (ammonia at reduced pressure) and oxygenated (air at atmospheric pressure) atmospheres under assistance of vacuum-ultraviolet (VUV) irradiation (use of a xenon silent discharge excimer source) or (ii) directly in air at atmospheric pressure using a dielectric-barrier discharge (DBD) device. After functionalization, the substrates were “activated” by dipping in a dilute acidic PdCl₂ solution or by spin-coating of a thin metal-organic film (from a solution of palladium acetate (PdAc) in chloroform). The catalytic activity of the so-deposited palladium species toward the electroless deposition of nickel was studied before and after a VUV post-irradiation (in air at atmospheric or reduced pressure) with a view to understanding better the role of the reducer (sodium hypophosphite) within the electroless bath.

This work confirms the specific interest of grafting nitrogenated functionalities onto polymer surfaces for attaching covalently the palladium-based catalyst (in particular in the case of the PdCl₂ route), forming thus strong Pd - N - C bonds at the metal/polymer interface. This results from the strong chemical affinity of palladium toward nitrogen. On the other hand, when oxygenated functionalities are surface-grafted, the conventional two-step procedure using SnCl₂ and PdCl₂ solutions can be proposed due to the strong chemical affinity of tin toward oxygen. The Ni deposits obtained under these different conditions pass the standard Scotch^®-tape test and, therefore, exhibit a good practical adhesion. For this same purpose, it is interesting to note that the DBD treatment operating in air at atmospheric pressure causes an increase of the surface roughness and, therefore, an improvement in adhesion of metallic films when their initiation is catalyzed through the PdAc route. In addition, this work demonstrates that extensive research still has to be performed to understand and improve the Ni/polymer adhesion when the PdAc route associated with a VUV irradiation is considered.     

Phosphonic acid‐containing polysulfones as anticorrosive layers

As a part of research work to elaborate polymeric materials for metal corrosion protection, we have developed a new family of phosphonic acid‐containing polymers. The synthesis and the characterization of polysulfones bearing alkyl phosphonate ester side groups are first described. These polymers are synthesized by direct polycondensation of a phosphonate ester‐containing bisphenol by aromatic nucleophilic substitution. The physicochemical properties of the resulting polymers are described. Acidic hydrolysis of phosphonate esters results in the formation of phosphonic acid groups. A series of phosphonic acid‐containing polysulfones is therefore obtained and characterized. A preliminary evaluation of the anticorrosive properties of these polymers is described. In 0.25M Na₂SO₄ solution, the corrosion rate of a polymer‐coated mild steel sample is much lower than of the free metal substrate. These results suggest that phosphonic acid‐containing polysulfones might be interesting as anticorrosive coatings. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41890.     

Thermoset composites functionalized with carbon nanofiber sheets for EMI shielding

Carbon nanofiber sheets were developed through filtering well‐dispersed carbon nanofiber (CNF) through filtering well‐dispersed aqueous solution of CNF particles with 0.4 μm hydrophilic polycarbonate membrane by the aid of high‐pressure air. They were used to functionalize composites by the resin transfer molding method. Their functionalized composites were characterized with scanning electron microscopy (SEM), four‐point probes and a vector network analyzer to measure their morphologies, electrical conductivity, and electromagnetic interference (EMI) shielding performance over the frequency range of 8–12 GHz (X band), respectively. Their morphologies show that CNF particles are overlapped and tightly connected with each other in their interconnected networks. The CNF sheets are exposed on the surface, although their networks are partially penetrated by polyester resins. Their electrical conductivity can be 3.0 ± 0.2 Scm^?1 or so, much higher by ten orders of magnitude than the reported electrical conductivity of CNF‐filled composites. Their EMI shielding effectiveness slightly varies in a range of ?30 dB to ?35 dB as a function of frequency, much higher than that of most CNF or carbon nanotube–filled composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41873.