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.     

Equilibrium,kinetics, and thermodynamics of Pd(II) adsorption onto poly(m‐aminobenzoic acid) chelating polymer

This study describes the equilibrium, kinetics, and thermodynamics of the palladium(II) (Pd(II)) adsorption onto poly(m‐aminobenzoic acid) (p‐mABA) chelating polymer. The p‐mABA was synthesized by the oxidation reaction of m‐aminobenzoic acid monomer with ammonium peroxydisulfate (APS). The synthesized p‐mABA chelating polymer was characterized by FTIR spectroscopy, gel permeation chromatography (GPC), thermal analysis, potentiometric titration, and scanning electron microscopy (SEM) analysis methods. The effects of the acidity, temperature, and initial Pd(II) concentration on the adsorption were examined by using batch adsorption technique. The optimum acidity for the Pd(II) adsorption was determined as pH 2. In the equilibrium studies, it was found that the Pd(II) adsorption capacity of the polymer was to be 24.21 mg/g and the adsorption data fitted better to the Langmuir isotherm than the Freundlich isotherm. The kinetics of the adsorption fitted to pseudo‐second‐order kinetic model. In the thermodynamic evaluation of the adsorption, the ΔG° values were calculated as ?16.98 and ?22.26 kJ/mol at 25–55°C temperatures. The enthalpy (ΔH°), entropy (ΔS°), and the activation energy (E_a) were found as 35.40 kJ/mol, 176.05 J/mol K, and 61.71 kJ/mol, respectively. The adsorption of Pd(II) ions onto p‐mABA was a spontaneous, endothermic, and chemical adsorption process which is governed by both ionic interaction and chelating mechanisms. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42533.     

Investigation on structure and properties of anion exchange membranes based on tetramethylbiphenol moieties containing copoly(arylene ether)s

Quaternary ammonium functionalized poly(arylene ether)s (QPAEs) containing 2,2′,6,6′‐tetramethylbiphenol moieties were designed and successfully synthesized via nucleophilic substitution polycondensation, bromination, quaternization and alkalization. The structure, water uptake, ion exchange capacities (IECs), hydroxide ion conductivities, and mechanical properties, as well as thermal and chemical stabilities of obtained QPAEs membranes were investigated. The QPAE‐a membrane with IEC value of 0.98 meq g^?1 demonstrated the highest ion conductivity (47.4 mS cm^?1) at 80°C. The ion transport activation energy (E_a) of QPAEs membranes varied from 8.57 to 19.95 kJ mol^?1. After chemical stability test conditioned in 1M NaOH at 60°C for 7 days, the QPAEs membranes except QPAE‐c (IEC = 0.88 meq g^?1) still exhibited high hydroxide ion conductivities (over 15 mS cm^?1) and acceptable tensile strength (～10 MPa). These properties indicate that the ionomers membranes are potential candidates for anion exchange membranes in anion exchange membrane fuel cells. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41525.     

Mild functionalization of carbon nanotubes filled epoxy composites: Effect on electromagnetic interferences shielding effectiveness

The effect of nitric acid mild functionalized multiwalled carbon nanotubes (MWCNTs) on electromagnetic interference (EMI) shielding effectiveness (SE) of epoxy composites was examined. MWCNTs were oxidized by concentrated nitric acid under reflux conditions, with different reaction times. The dispersion of MWCNTs after functionalization was improved due to the presence of oxygen functional groups on the nanotubes surface. Functionalization at 2 h exhibits the highest EMI SE and electrical conductivity of MWCNTs filled epoxy composites. However, EMI shielding performance of MWCNTs filled epoxy composite declined when the functionalization reaction time was prolonged. This was due to extensive damage on the MWCNT structure, as verified by a Raman spectroscope. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42557.     

Dendrimer functionalized polysilane: An efficient and recyclable organocatalyst

Polysilane supported dendrimer was efficiently utilized as an organocatalyst for Knoevenagel condensation reaction. Polysilane support was synthesized by the polymerization of trichloromethylsilane. The polypropyleneimine (PPI) dendrimer was grafted on the polymer support by divergent method. The dendrimer was synthesized up to three generations (G3). The dendrimer functionalized polysilane (PS‐PPIG3) was found to contain high concentration of terminal amino groups. The catalytic activity of the PS‐PPIG3 dendrimer was generalized by conducting the Knoevenagel condensation reaction with diverse sets of substrates, and was found to be an efficient organocatalyst. The condensation product could be easily separated from the reaction medium because of the heterogeneous nature of the polymer support. The reaction conditions were optimized, and the catalyst was found to be reusable. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41593.     

Functionalization of hybrid poly(n‐isopropylacrylamide) hydrogels for Escherichia coli cell capture via adsorbed intermediate dye molecule

Poly(n‐isopropylacrylamide) Laponite (PNIPAM‐Lap) hybrid hydrogels, which use the synthetic clay Laponite as a crosslinker, permanently adsorb cationic laser dyes out of solution. This proof‐of‐concept expounds on this capability by adsorbing an intermediate dye molecule and using it as the foundation for successfully conjugating microbial antibodies to the surface of a PNIPAM hydrogel. The study involves using acriflavinium chloride molecules, adsorbed by a PNIPAM‐Lap hydrogel from an acriflavine laser dye solution, as an intermediate molecule to attach antibodies raised against E. coli to the hydrogel and demonstrate cell capture. Furthermore, this system exemplifies a novel biotechnological platform for greatly expanding PNIPAM hydrogels' capabilities and applicability through conjugation chemistry to surface‐bound molecules. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41557.     

Synthesis and application of streptavidin functionalized organosilica microparticles

This article reports on the chemical synthesis, functionalization and application of streptavidin (SA)‐coated organosilica microparticles. Thiol‐functionalized organosilica microparticles are synthesized via a two‐step approach involving acid‐catalyzed hydrolysis and condensation of 3‐mercaptopropyl trimethoxysilane (MPS), followed by base‐catalyzed condensation. The surfaces of these particles are modified with 3‐aminopropyltriethoxysilane (APS), and characterized by FTIR, XPS, and TGA. Then, APS‐functionalized microparticles are covalently coated with SAs by using glutaraldehyde as a coupling agent, and characterized by FTIR, SEM, and AFM. Immobilization of biotinylated λ DNA onto microparticles via SA‐biotin immuoreaction is confirmed by confocal microscopy. The results show that these SA‐functionalized organosilica microparticles are useful carriers for DNA manipulation at the single molecule level. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41560.     

Facile synthesis of functional copolymers with pendant vinyl groups by using asymmetrical divinyl monomers

Polymers bearing pendant vinyl groups have attracted significant attraction because they can be further modified for required applications, but their syntheses are still a big challenge. Herein, allyl methacrylate was catalyzed using a phosphazene base to homopolymerize or copolymerize with 2‐(N, N‐dimethylamino) ethyl methacrylate, affording vinyl functional polymers, which were further successfully tailored by the thiol–ene coupling reaction. The result showed that both the homopolymerizations and copolymerizations could proceed at room temperature with very high monomer conversions. The contents of pendant double bonds in the copolymers were approximately equal to the monomer feeds, but the LCST of the statistical copolymers linearly decreased with increasing AMA content. This strategy offered a new scalable and facile strategy for vinyl functional polymers, would have a wide practical application in many fields. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42758.