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The conformal deposition of metal nanoparticles (Au, Pd, and Pt) onto natural cellulose fibers using two chemical strategies is reported. The driven mechanism responsible for the high surface coverage of the substrates was identified as the electrostatic interactions between the positively charged cellulose and the either negatively charged nanoparticles or negative metal complex ions. The natural cellulose fibers were rendered cationic by grafting ammonium ions, using an epoxy substitution reaction, to the abundant hydroxyl groups present in cellulose molecules. The first method involved the electrostatic assembly of citrate-stabilized metal nanoparticles directly onto the cationic surfaces of cellulose. The second method involved the adsorption of negative metal complex ions onto the cationic cellulose followed by a reduction reaction. The attained metal nanoparticles bound with cellulose fibers were characterized by electron microscopy (TEM and SEM) and energy-dispersive X-ray spectroscopy (EDX). Both pathways generated metal nanoparticles with high packing densities on the cellulose substrates even when very dilute solutions of metal colloids or metal salts were used. Achieving high surface coverage with low-concentration precursor solutions may open an avenue for the production of flexible catalytic mantles or highly functionalized textile substrates.
ACS Appl Mater Interfaces 2009 Apr
PMID:Metal nanoparticles on natural cellulose fibers: electrostatic assembly and in situ synthesis. 2035 4

In recent years, cellulose-based materials have attracted significant attention. To broaden the application areas for cellulose, polymers are often grafted to/from the surface to modify its properties. This study applies ARGET (activators regenerated by electron transfer) ATRP (atom transfer radical polymerization) when straightforwardly grafting methyl methacrylate (MMA), styrene (St), and glycidyl methacrylate (GMA) from cellulose in the form of conventional filter paper in the presence of a sacrificial initiator. The free polymer, formed from the free initiator in parallel to the grafting, was characterized by (1)H NMR and SEC, showing that sufficient control is achieved. However, the analyses also indicated that the propagation from the surface cannot be neglected compared to the propagation of the free polymer at higher targeted molecular weights, which is an assumption often made. The grafted filter papers were evaluated with FT-IR, suggesting that the amount of polymer on the surface increased with increasing monomer conversion, which the FE-SEM micrographs of the substrates also demonstrated. Water contact angle (CA) measurements implied that covering layers of PMMA and PS were formed on the cellulose substrate, making the surface hydrophobic, in spite of low DPs. The CA of the PGMA-grafted filter papers revealed that, by utilizing either aprotic or protic solvents when washing the substrates, it was possible to either preserve or hydrolyze the epoxy groups. Independent of the solvent used, all grafted filter papers were essentially colorless after the washing procedure because of the low amount of copper required when performing ARGET ATRP. Nevertheless, surface modification of cellulose via ARGET ATRP truly facilitates the manufacturing since no thorough freeze-thaw degassing procedures are required.
ACS Appl Mater Interfaces 2009 Nov
PMID:ARGET ATRP for versatile grafting of cellulose using various monomers. 2035 39

Dialkyldithiophosphates (DTPs) of zinc(II), copper(II), and other metals have been extensively used as multifunctional additives in lubricants to control friction and reduce wear in mechanical systems. Among these DTP compounds, zinc dialkyldithiophosphates (ZnDTPs) are the most common additives extensively used for more than 60 years. These additives form a protective film on steel surfaces and, thus, control friction and reduce wear. However, ZnDTPs contain zinc and large amounts of phosphorus and sulfur, which impair the environment, both directly and indirectly, by adversely affecting the performance of catalytic converters of various automobiles. For this reason, environmental legislation imposes limitations on concentrations of phosphorus, sulfur, and zinc in the lubricants. In this work, we report on zinc-free S-di-n-octoxyboron-O,O'-di-n-octyldithiophosphate (DOB-DTP) lubricant additive with amount of phosphorus and sulfur reduced by half in a molecule as compared with ZnDTPs. DOB-DTP was synthesized by a reaction in two steps under inert nitrogen atmosphere. The final product, a viscous liquid, was characterized by the elemental analysis, FT-IR, multinuclear (1)H, (13)C, (31)P, and (11)B NMR spectroscopy and thermal analyses. Tribological performance of a mineral oil with this new additive was evaluated in comparison with O,O'-di-n-butyl-dithiophosphato-zinc(II) (ZnDTP) using a four-ball tribometer. The surface morphology and the elemental composition of the tribofilms were characterized using scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDS). The results show that DOB-DTP has a considerably better antiwear performance and higher stability of the coefficient of friction with time as compared with ZnDTP. Both phosphorus and sulfur were detected by the EDS on the worn steel surfaces at all concentrations of additives in the base oil.
ACS Appl Mater Interfaces 2009 Dec
PMID:Synthesis, physicochemical, and tribological characterization of S-Di-n-octoxyboron-O,O'-di-n-octyldithiophosphate. 2035 64

Continuous nickel oxide (NiO) nanocomposite layer on flexible polyimide (PI) substrate was prepared via an ion exchange technique. First, nickel(Pi) poly(amate) layers were formed on both surfaces of PI film through chemical surface modification of PI films in aqueous NaOH solution and then ion exchange in aqueous NiSO4 solution. Subsequently, hydrothermal treatment of the Ni2+-loaded PI films in an aqueous urea solution led to Ni(OH)2 formation in the surface-modified layers. Final thermal annealing in ambient air made Ni(OH)2 decompose to NiO, which diffused and aggregated to give continuous layers on both surfaces of PI film. The composite films were characterized by XRD, XPS, SEM, TEM, TGA, and DSC, respectively. Results from SEM and TEM measuring revealed that the NiO layers consisted of NiO nanoparticles with diameter ranging from 10 to 15 nm. Thermal properties of PI/NiO nanocomposite films were similar to those of host PI. This paper provides an effective methodology for the preparation of polymer/metal oxide nanocomposite films, which hold great promise toward the potential application in the areas of flexible microsensors and devices.
ACS Appl Mater Interfaces 2010 Jan
PMID:Fabrication of nickel oxide nanocomposite layer on a flexible polyimide substrate via ion exchange technique. 2035 27

Electrostatic layer-by-layer assembly was the basis for the synthesis of multilayer nanorod/polymer composite films. Cationic and water-soluble CdSe nanorods (NRs) were synthesized and partnered with anionic polymers including poly(sodium 4-styrenesulfonate) (PSS) and two polythiophene-based photoactive polymers, sodium poly[2-(3-thienyl)-ethoxy-4-butylsulfonate (PTEBS) and poly[3-(potassium-6-hexanoate)thiophene-2,5-diyl] (P3KHT). Controlled multilayer growth is shown through UV-vis spectroscopy, cross-sectional SEM and surface analytical techniques including atomic force microscopy. The formation of an intimate nanorod/conducting polymer bulk heterojunction is confirmed through cross-sectional SEM, TEM, and scanning Auger analysis. A series of photovoltaic devices was fabricated on ITO electrodes using CdSe NRs in combination with PTEBS or P3KHT. A thorough device analysis showed that performance was limited by low short circuit current although charge transfer was confirmed in the ELBL nanocomposite thin films.
ACS Appl Mater Interfaces 2010 Jan
PMID:Electrostatic layer-by-layer assembly of CdSe nanorod/polymer nanocomposite thin films. 2035 38

Hybrid nanocomposites containing carbon nanotubes (CNTs) and ordered polyaniline (PANI) have been prepared through an in situ polymerization reaction using a single-walled nanotube (SWNT) as template and aniline as reactant. TEM, SEM, XRD, and Raman analyses show that the polyaniline grew along the surface of CNTs forming an ordered chain structure during the SWNT-directed polymerization process. The SWNT/PANI nanocomposites show both higher electrical conductivity and Seebeck coefficient as compared to pure PANI, which could be attributed to the enhanced carrier mobility in the ordered chain structures of the PANI. The maximum electrical conductivity and Seebeck coefficient of composites reach 1.25 x 10(4) S m(-1) and 40 microV K(-1), respectively, and the maximum power factor is up to 2 x 10(-5) W m(-1) K(-2), more than 2 orders of magnitude higher than the pure polyaniline. This study suggests that constructing highly ordered chain structure is a novel and effective way for improving the thermoelectric properties of conducting polymers.
ACS Nano 2010 Apr 27
PMID:Enhanced thermoelectric performance of single-walled carbon nanotubes/polyaniline hybrid nanocomposites. 2035 34

A glass substrate, coated with a Parylene film, was coated with ZnO by three different methods: ultrasound, microwave, and microwave-plasma irradiation. These coating modes are simple, efficient, and environmentally friendly one-step processes. The structure of the coated products was characterized and compared using methods such as XRD, HR-SEM, EDS, RBS, and optical spectroscopy. Coating by ZnO nanoparticles was achieved for all three approaches. The products were found to differ in their particle sizes, coating thickness, and depth of penetration. All of the ZnO-Parylene-glass composites demonstrated a significant antibacterial activity against Escherichia coli (Gram negative) and Staphylococcus aureus (Gram positive) strains.
ACS Appl Mater Interfaces 2010 Apr
PMID:Decorating parylene-coated glass with ZnO nanoparticles for antibacterial applications: a comparative study of sonochemical, microwave, and microwave-plasma coating routes. 2035 39

A new, efficient, palladium- and chromium-free process for the electroless plating of acrylonitrile-butadiene-styrene (ABS) polymers has been developed. The process is based on the ion-exchange properties of poly(acrylic acid) (PAA) chemically grafted onto ABS via a simple and one-step method that prevents using classical surface conditioning. Hence, ABS electroless plating can be obtained in three steps, namely: (i) the grafting of PAA onto ABS, (ii) the copper Cu(0) seeding of the ABS surface, and (iii) the nickel or copper metallization using commercial-like electroless plating bath. IR, XPS, and SEM were used to characterize each step of the process, and the Cu loading was quantified by atomic absorption spectroscopy. This process successfully compares with the commercial one based on chromic acid etching and palladium-based seed layer, because the final metallic layer showed excellent adhesion with the ABS substrate.
ACS Appl Mater Interfaces 2010 Apr
PMID:ABS polymer electroless plating through a one-step poly(acrylic acid) covalent grafting. 2036 51

The photochemical method is a convenient and simple way to synthesize the polymer brush on surface. We presented here a facile approach to fabricate PMMA brush on silica particles (SPs) by combination of self-assembly monolayer of hyperbranched polymeric thioxanthone (HPTX) and surface-initiated photopolymerization (SIPP). HPTX was immobilized on the surface of silica particles (SPs) through nucleophilic addition between amine and epoxy groups, and then initiated photopolymerization of MMA to generate PMMA brush on SPs at room temperature. The whole process was well-traced by FT-IR, TGA, SEM, and TEM. The results show that it is easy to create PMMA brushes of tunable thickness under UV irradiation. Especially, TEM images reveal the obvious formation of well-defined hybrid particles with SPs as the core and PMMA layers as the shell. The obtained hybrid particles can be implanted into PMMA matrix to produce PMMA composite with enhanced thermal and mechanical properties.
ACS Appl Mater Interfaces 2010 Apr
PMID:Well-defined PMMA brush on silica particles fabricated by surface-initiated photopolymerization (SIPP). 2042 23

Polymer-derived ceramic fibers with aligned multiwalled carbon nanotubes (MWCNTs) are fabricated through the electrospinning of polyaluminasilazane solutions with well-dispersed MWCNTs followed by pyrolysis. Poly(3-hexylthiophene)-b-poly (poly (ethylene glycol) methyl ether acrylate) (P3HT-b-PPEGA), a conjugated block copolymer compatible with polyaluminasilazane, is used to functionalize MWCNT surfaces with PPEGA, providing a noninvasive approach to disperse carbon nanotubes in polyaluminasilazane chloroform solutions. The electrospinning of the MWCNT/polyaluminasilazane solutions generates polymer fibers with aligned MWCNTs where MWCNTs are oriented along the electrospun jet by a sink flow. The subsequent pyrolysis of the obtained composite fibers produces ceramic fibers with aligned MWCNTs. The study of the effect of polymer and CNT concentration on the fiber structures shows that the fiber size increases with the increment of polymer concentration, whereas higher CNT content in the polymer solutions leads to thinner fibers attributable to the increased conductivity. Both the SEM and TEM characterization of the polymer and ceramic fibers demonstrates the uniform orientation of CNTs along the fibers, suggesting excellent dispersion of CNTs and efficient CNT alignment via the electrospinning. The electrical conductivity of a ceramic fibers with 1.2% aligned MWCNTs is measured to be 1.58 x 10(-6) S/cm, which is more than 500 times higher than that of bulk ceramic (3.43 x 10(-9) S/cm). Such an approach provides a versatile method to disperse CNTs in preceramic polymer solutions and offers a new approach to integrate aligned CNTs in ceramics.
ACS Appl Mater Interfaces 2010 Apr
PMID:Polymer-derived ceramic composite fibers with aligned pristine multiwalled carbon nanotubes. 2042 34


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