A novel synthesis route for a gold–polymer soft composite material

We report on the synthesis of a metal–polymer composite material using an interfacial polymerization approach. The advantage of this approach is to form an intimate contact be‐tween the metal and polymer, which is an important param‐ eter for the synthesis of a nanocomposite material. It was found that polymerization of o‐phenylenediamine (PDA) us‐ing HAuCl₄ as an oxidizing agent leads to the formation of poly‐PDA with a fiber‐like morphology, while the reduction of HAuCl₄ results in the formation of well dispersed and sta‐bilized gold nanoparticles within the polymer matrix. The synthesis was carried out at the organic–aqueous interface. The resultant composite material was purely hydrophilic in nature and deposited at the aqueous fraction of the reaction medium. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The Effect of Cross‐Linking on the Actuation of an Electroactive IPMC Prepared with a Fluorinated Acrylic Copolymer

The hydroxyl group of HEMA was cross‐linked with 1,3‐diethoxy‐1,1,3,3‐tetramethyldisiloxane in order to enhance the actuation force of the ionic polymer‐metal composite (IPMC) made from the acrylic ter‐polymer of fluoroalkyl methacrylate, 2‐acylamido‐2‐methyl‐1‐propanesulfonic acid, and 2‐hydroxyethyl methacrylate (HEMA). The water uptake was reduced and the mechanical strengths of the membrane were improved by the cross‐linkage. The actuation force of the IPMC was generally enhanced, although it was reduced somewhat at high levels of cross‐linking. The current and deformation responses of the IPMC were both decreased by cross‐linking.     

Plasma‐Substrate Interaction during Plasma Deposition on Polymers

The initial stage of film growth during plasma deposition on polymers determines many film properties such as morphology and structure, interphase formation and adhesion. Therefore, the plasma‐substrate interaction is investigated regarding the energy density during film growth, which is defined by the energy flux per depositing atom. The flux of film‐forming species and the flux of energetic particles were determined for metal sputtering (silver films) and plasma polymer deposition (amino‐functional hydrocarbon films). It is shown that enhanced energy densities can be obtained during the initial film growth due to reduced deposition rates and mixing with the polymer substrate (interphase formation). Thus, good adhesion on polymers such as polyethylene terephthalate (PET) has been achieved. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Diffusion and Growth of Metal Clusters in Nanocomposites: A Kinetic Monte Carlo Study

Noble metals that are deposited on a polymer surface exhibit surface diffusion and diffusion into the bulk. At the same time the metal atoms tend to form clusters because their cohesive energy is about two orders of magnitude higher than the cohesive energy of polymers. To selfconsistently simulate these coupled processes, we present in this paper a Kinetic Monte Carlo approach. Using a simple model with diffusion coefficients taken as input parameters allows us to perform a systematic study of the behavior of a large ensemble of metal atoms on a polymer surface eventually leading to polymer nanocomposites. Special emphasis is placed on the cluster growth, cluster size distribution and the penetration of clusters into the substrate. We also study the influence of surface defects and analyze how the properties of the resulting material can be controlled by variation of the deposition rate (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Fabrication of 6,13‐bis(triisopropyl‐silylethynyl)–pentacene thin‐film transistors with the silver ink transfer method using a polymer stamp

We fabricated 6,13‐bis(triisopropylsilylethynyl)–pentacene (TIPS–pentacene) thin film transistors using a direct metal transfer method. Using different metals, such as Au and Ag ink, electrode patterns are formed from the relief region of the polymer mold. TIPS–pentacene TFTs using the Ag ink transfer method show a similar performance to those using the Au metal transfer method. This method has advantages over the Au metal transfer method because it does not require vacuum equipment and a dry etching process. The self‐assembled monolayer (SAM) treated device exhibits a carrier mobility of 9.5 × 10^–2 cm²/V · s, and an on/off ratio of 4.6 × 10⁴. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Phosphonated Polyethylenimine‐Coated Nanoparticles: Size‐ and Zeta‐Potential‐Adjustable Nanomaterials

Novel partially phosphonated polyethylenimine polymers are developed in order to control the modification of nanoparticle (NP) surfaces. This polymer is built by an accessible one‐step process. The numerous phosphonate functions assume both a strong covalent anchoring on metal oxide NPs and a modulation of electric charges, while amino groups are associated with dispersion preservation and subsequent biofunctionalization. The zwitterionic nanomaterials obtained display a good stability toward pH and ionic strength. According to the selected percentage of phosphonation and the polymer size, zeta potential, and diameter of the particles are controlled.     

A spectral-kinetic investigation of the negative photochromism of systems based on complexes of spiropyrans with metal ions

A comparative spectral-kinetic study of the negative photochromism of complexes of molecules of nitrosubstituted indoline spiropyrans with metal ions in solutions and polymer matrices is carried out. The possibility of creating polymer coatings with negative photochromism, based on the complexes of spiropyran molecules with metal ions is shown for the first time. It is determined that the efficiency of photochromic transformations of complexes depends on the nature of the polymer binder, the component composition of the polymer film, and the properties of metal cations. During the storage of photochromic polymer films in the dark, a spectral manifestation of the transformation of metal complexes into putative protonated complexes is revealed. It is found that the stability of the complexes is determined by the nature of the polymer binder and the affinity of the metal cations to an electron.     

Fluorescence Spectroscopy of Polymer Systems Doped with Rare-Earth Metal Ions and Their Complexes

Abstract

There has been an increased attention to explore the possibility of using polymer materials with rare-earth (RE) metal ions and their complexes as potential optical materials due to their capability of exhibiting novel and unusual properties. The fluorescence characteristics of polymer systems doped with RE metal ions and/or their complexes were analyzed and the effects of the doping metal ion/metal complexes as well as nature of the material were discussed. Electron transitions of REs can be manipulated by efficient ligand designs and proper doping into the polymer matrix. Emphasis was especially focused on the accommodation of the metal ion/metal complex in polymer matrix as well as its role in fluorescence. The photochemistry of the fluorescent polymer matrices with RE complexes is expected to open up frontier fields that lie between photophysics and materials science. Recent developments on a new aspect of these technologies related to the fluorescence dynamics in polymer analysis will also be discussed in this present review.     

Efficiency Improvement in Polymer Light‐Emitting Diodes by “Far‐Field” Effect of Gold Nanoparticles

The “far‐field” effect of metal nanoparticles (NPs), when chromophores localized nearby metal NPs (typically the distance >λ/10), is an important optical effect to enhance emission in photoluminescence. The far‐field effect originates mainly from the interaction between origin emission and mirror‐reflected emission, resulting in the increased irradiative rate of chromophores on the mirror‐type substrate. Here, the far‐field effect is used to improve emission efficiency of polymer light‐emitting diodes (PLEDs). A universal performance improvement is achieved for the full visible light (red, green, blue) PLEDs, utilizing gold (Au) NPs to modify the indium tin oxide (ITO) substrates; this is shown by experimental and theoretical simulation to mainly come from the far‐field effect. The optimized distance, between the NPs and chromophores with visible light emission ranging from 400 to 700 nm, is 80–120 nm. Thus the scope of the far‐field may overlap the light‐emitting profile very well to enhance the efficiency of optoelectronic devices. The 30–40% enhancement is obtained for different color‐emitting materials through distance optimization. The far‐field effect is demonstrated to enhance device performance for materials in the full‐visible spectral range, which extends the optoelectric applications of Au NPs.     

一维铁磁/有机系统的基态与自旋分布研究

文中用一维紧束缚模型描述铁磁金属,用一维非简并的Su-Schrieffer -Heeger (SSH)模型描述共轭聚合物,研究了在一维铁磁/共轭聚合物系统和一维CMR材料/ 聚合物系统中的电子转移和自旋转移.发现在聚合物部分没有自旋的双极化子比有自旋的极化子具有较低的能量而容易产生.然而在铁磁CMR材料/聚合物系统中极化子的产生能低于聚合物中极化子的产生能,增加了有机物中自旋极化输运的可能性.     

Long-range surface plasmon polaritons with subwavelength mode expansion in an asymmetrical system

Long-range surface plasmon polariton (LRSPP) modes in an asymmetrical system, in which the thin metal film is sandwiched between a semi-infinite substrate and a high permittivity polymer film with a finite thickness, are theoretically calculated and analyzed. Due to the high permittivity of the polymer film, at proper polymer film thicknesses, the index-matching condition of the dielectrics at both sides of the metal can be satisfied for supporting LRSPP modes, and the electromagnetic field above the metal can be localized well. It is found that these LRSPP modes have both long propagation lengths and subwavelength mode expansion above the metal at the optimal polymer film thicknesses. Furthermore, the requirements on the refractive index and the thickness of the polymer film to support LRSPP modes at the optimal thicknesses are found to be not critical.     

The 3D Nanoscale Evolution of Platinum–Niobium Oxide Fuel Cell Catalysts via Identical Location Electron Tomography

Current state‐of‐the‐art catalysts for polymer electrolyte membrane fuel cells, comprised of platinum nanoparticles on a high surface area carbon support, are susceptible to platinum dissolution and carbon support corrosion during operation. The use of transition metal oxides in the support material is proposed to stabilize the catalyst material by minimizing platinum dissolution and carbon corrosion. Here, the 3D structural changes are tracked for a hybrid Pt–Nb oxide on carbon catalyst before and after potential cycling utilizing identical location electron tomography. Pt dissolution is observed to varying degrees in both high and low Nb oxide content structures and appreciable carbon support corrosion in the high Nb oxide content structure but not in the low Nb oxide structure.     

Polymer‐free,low tension graphene mechanical resonators

Graphene resonators are fabricated using a polymer‐free, direct transfer method onto metal reinforced holey carbon grids. The resonators are distinguished by the absence of organic residues and excellent crystallinity. The normal mode frequencies are measured using a Fabry–Perot technique; resonance curves indicate highly linear behaviour but very little built‐in strain, which is consistent with device geometry examined by atomic force microscopy. We conclude that the oscillators' restoring force is due instead to graphene's intrinsic bending rigidity; our measurements indicate a value of approximately 1.0 eV, consistent with previous theoretical and experimental work. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Wetting, Bonding and Interfacial Energy of Nanocrystalline Metal Particles on Crystalline DCH Polymer and Amorphous Carbon Substrates

Experimental results concerning the interaction between a variety of nanocrystalline metals (gold, silver, nickel and chromium) and both crystalline polymer [poly-DCH (1,6-di (N-carbazolyl)-2,4-hexadiene)] and amorphous carbon substrates, are presented and analyzed. Attention is focused on aspects of the interaction that concern interfacial bonding, its correlation with the cohesive energies of the various metals and the energy of the interfaces. Experimental contributions include qualitative estimates of the magnitude of interfacial energies for the crystalline polymer/metal and amorphous carbon/metal interfaces and a direct measurement of the interfacial energies for gold and silver nanocrystals deposited on the amorphous carbon substrate. The sequence of interfacial energy values for the polymer/metal and amorphous carbon/metal systems is also determined. The interfacial energies for both the poly-DCH and amorphous carbon substrates decreases in the order silver, gold, nickel, and chromium, as expected from cohesive energy, melting point and surface energy data for these elements. The crystalline polymer/metal interfaces were examined for the presence of orientation relationships using selected area diffraction and optical diffractometry of high-resolution TEM images. No orientation relationships were found for any of the polymer/metal combinations spanning a large range of metal reactivities. Lack of atomic matching or some as yet unknown surface condition on the polymer may be responsible for this effect.     

Nanostructural self-organization and dynamic adaptation of metal–polymer tribosystems

The results of investigating the effect of nanosize modifiers of a polymer matrix on the nanostructural self-organization of polymer composites and dynamic adaptation of metal–polymer tribosystems, which considerably affect the wear resistance of polymer composite materials, have been analyzed. It has been shown that the physicochemical nanostructural self-organization processes are developed in metal–polymer tribosystems with the formation of thermotropic liquid-crystal structures of the polymer matrix, followed by the transition of the system to the stationary state with a negative feedback that ensures dynamic adaptation of the tribosystem to given operating conditions.     

Heterogeneous Nanoassembling: Microfluidically Prepared Poly(methyl methacrylate) Nanoparticles on Ag Microrods and ZnO Microflowers

The heterogeneous assembly of colloidal polymer particles on the nano‐ and microstructures of a metal is a versatile platform for adjusting the mechanical and electrical properties simultaneously. The assemblies of silver (Ag) microrods and flower‐like zinc oxide (ZnO) microparticles with poly(methyl methacrylate) (PMMA) nanospheres are presented to prepare advanced composite materials. PMMA nanoparticles are prepared via the emulsion polymerization technique using a microfluidic preparation step in the presence of cationic surfactant. The surface charge of PMMA particles determines the binding interaction strength with inorganic constituents. Ag microrods and ZnO microparticles are prepared in a batch and in a continuous flow process, respectively. The assembling process can be explained by a particle–particle binding process due to the electrostatic interaction for both types of nanoassemblies. The observed binding pattern reveals certain lateral mobility of the small polymer particles at the surface of larger metal particle. The particle ratios in the nanoassemblies can be tuned over a wide range by changing the reaction parameters.     

Electrical conductivity of chelate polymers. I

The electrical conductivity of 8-hydroxyquinoline-formaldehyde (8HQ-F) polymer sample and its several metal chelates is measured at different temperatures. All the polymeric metal chelates are found as semiconductors. The electrical conductivity of polymeric chelates depends only on the nature of the metal ions and is higher than that of the parent polymer sample due to incorporation of metal atoms in its structure.     

Formation dynamics of bipolaron in a metal/polymer/metal structure

Charge injection process from metal electrode to a nondegenerate polymer in a metal/ polymer/ metal structure has been investigated by using a nonadiabatic dynamic method. We demonstrate that the dynamical formation of a bipolaron sensitively depends on the strength of applied electric field, the work function of metal electrode, and the contact between the polymer and the electrode. For a given bias applied to one of the electrode (V₀) and coupling between the electrode and the polymer (t^′), such as V₀=0.79 eV and t^′=1 eV, the charge injection process depending on the electric field can be divided into the following three cases: (1) in the absence of the electric field, only one electron tunnels into the polymer to form a polaron near the middle of the polymer chain; (2) at low electric fields, two electrons transfer into the polymer chain to form a bipolaron; (3) at higher electric fields, bipolaron can not be formed in the polymer chain, electrons are transferred from the left electrode to right electrode through the polymer one by one accompanying with small irregular lattice deformations.     

Optical properties of nanocomposites based on polymers and metal nanoparticles

The optical properties of nanocomposites of metal nanoparticles and polymers of two types have been studied. Gold and silver nanoparticles were obtained by laser ablation of corresponding metal targets in acetone and chloroform. The thus formed colloidal solutions were used to prepare nanocomposites of these nanoparticles in polymer matrices of polymethylmethacrylate (PMMA) and fluorine-containing polymer LF-32. The polymer matrix is found to promote aggregation of the metal nanoparticles under study into elongated chains. In turn, metal nanoparticles affect the polymer matrix. In the case of PMMA, suppression of the vibrational peaks of polymer in the low-frequency region of its Raman spectrum occurs. In the case of LF-32, gold and silver nanoparticles amplify the Raman signal of the polymer matrix. In addition, the Raman spectra of nanocomposites indicate aggregation of disordered carbon around the nanoparticles obtained by laser ablation in organic solvents. The possibilities of studying the ultrafast (about 1 ps) optical response of the nanocomposites obtained in order to use it in photonics elements are discussed.     

Complexation of bis‐crown stilbene with alkali and alkaline‐earth metal cations. Ultrafast excited state dynamics of the stilbene‐viologen analogue charge transfer complex

The complex formation of bis(18‐crown‐6)stilbene ( 1 ) and its supramolecular donor‐acceptor complex with N,N′‐bis(ammonioethyl) 1,2‐di(4‐pyridyl)ethylene derivative ( 2 ) with alkali and alkaline‐earth metal perchlorates has been studied using absorption, steady‐state fluorescence, and femtosecond transient absorption spectroscopy. The formation of 1 ?Mⁿ⁺ and 1 ?(Mⁿ⁺)₂ complexes in acetonitrile was demonstrated. The weak long‐wavelength charge‐transfer absorption band of 1 · 2 completely vanishes upon complexation with metal cations because of disruption of the pseudocyclic structure. The spectroscopic and luminescence parameters, stability constants, and 2‐stage dissociation constants were calculated. The initial stage of a recoordination process was found in the excited complexes 1 ?M⁺ and 1 ?(M⁺)₂ (M = Li, Na). The pronounced fluorescence quenching of 1 · 2 is explained by very fast back electron transfer (τ_et = 0.397 ps). The structure of complex 1 · 2 was studied by X‐ray diffraction; stacked ( 1 · 2 )_m polymer in which the components were connected by hydrogen bonding and stacking was found in the crystal. These compounds can be considered as novel optical molecular sensors for alkali and alkaline‐earth metal cations.