Stimuli-responsive polyelectrolyte block copolymer brushes synthesized from the si wafer via atom-transfer radical polymerization

Surface-tethered oppositely charged weak polyelectrolyte block copolymer brushes composed of poly(2-vinyl pyridine) (P2VP) and poly(acrylic acid) (PAA) were grown from the Si wafer by atom-transfer radical polymerization. The P2VP-b-PAA brushes were prepared through hydrolysis of the second PtBA block to the corresponding acrylic acid. The P2VP-b-PAA brushes with different PAA block length were obtained. The P2VP-b-PAA brushes revealed a unique reversible wetting behavior with pH. The difference between the solubility parameters for P2VP and PAA, the changes of surface chemical composition and surface roughness, and the reversible wetting behavior illustrated that the surface rearrangement occurred during treatment of the P2VP-b-PAA brushes by aqueous solution with different pH value. The reversible properties of the P2VP-b-PAA brushes can be used to regulate the adsorption of the sulfonated PS nanoparticles.

In-situ fabrication of hybrid polyoxometalate nanoparticles composite films

inorganic-organic hybrid nanoparticles multilayer films were fabricated by extending the method of nucleation and growth of particles in polymer assemblies. The polyelectrolyte matrix was constructed by layer-by-layer self-assembly method. Synthesis of polyoxometalate nanoparticles was achieved by alternately dipping the precursor polyelectrolyte matrix into AgNO3 and H4SiW12O40 aqueous solutions. Repeating the above synthesis process, Ag4SiW12O40 nanoparticles with controllable diameters of 20 to 77 nm were synthesized in the multilayer films in-situ. UV-vis absorption spectra indicate that the nanoparticles grew gradually in the synthesis process. Transmission electron microscopy was used to observe the size and morphology of the nanoparticles.

One-step synthesis and characterization of polyelectrolyte-protected gold nanoparticles through a thermal process

Polyelectrolyte-protected gold nanoparticles have been facilely obtained by heating an amine-containing polyelectrolyte/HAuCl4 aqueous solution without the additional step of introducing other reducing agents. All experimental data indicate that different initial molar ratio of polyelectrolyte to gold can lead to the formation of dispersed nanoparticles, quasi one-dimensional aggregates of nanoparticles or bulk metal deposits. More importantly, the growth kinetics of gold particles thus formed can be tuned by changing the initial molar ratio of polyelectrolyte to gold.

Photochromic inorganic-organic multilayer films based on polyoxometalates and poly(ethylenimine)

Novel photochromic inorganic-organic multilayers composed of polyoxometalates and poly(ethylenimine) have been prepared by the layer-by-layer (LbL) self-assembly method. The growth process, composition, surface topography, and photochromic properties of the multilayer films were investigated by UV-visible and Fourier transform infrared spectroscopy, atomic force microscopy, electrospin resonance (ESR), and X-ray photoelectron spectroscopy (XPS). Irradiated with ultraviolet light, the transparent films changed from colorless to blue. Moreover, the blue films showed good reversibility of photochromism, and could recover the colorless state gradually in air, where oxygen plays an important role in the bleaching process. On account of the ESR and XPS results, parts of W6+ in multilayers were reduced to W5+, which exhibited a characteristic blue; a possible photochromic mechanism can be speculated. This work provides basic guideline for the assembly of multilayers with photochromic properties.

Polyhedral oligomeric silsesquioxane nanocomposite thin films via layer-by-layer electrostatic self-assembly

Fabrication of ultrathin polymer composite films with low dielectric constants has been demonstrated. Octa( aminophenyl) silsesquioxane (OAPS) was synthesized and assembled with poly( acrylic acid) (PAA) and poly( styrene sulfonate) (PSS) via a layer-by-layer electrostatic self-assembly technique to yield nanoporous ultrathin films. The OAPS was soluble in water at pH 3 or lower, and suitable pH conditions for the OAPS/PAA and OAPS/PSS assemblies were determined. The multilayer formation process was studied by contact angle analysis, X-ray photoelectron spectroscopy, atomic force microscopy, quartz crystal microgravimetry, UV-vis spectroscopy, and ellipsometry. The multilayer growth was found to be steady and uniform, and the analysis of the film surface revealed a rough topography due to OAPS aggregates. The incorporation of porous OAPS molecules into the thin films significantly lowered their dielectric constants. The OAPS/PAA multilayer thin film thus prepared exhibited a dielectric constant of 2.06 compared to 2.58 for pure PAA film. The OAPS/PAA multilayer film was heated to effect cross-linking between the OAPS and the PAA layers, and the transformation was verified by reflection-absorption Fourier transform infrared spectroscopy.

One-step polyelectrolyte-based route to well-dispersed gold nanoparticles: Synthesis and insight

Polyelectrolytes have been widely used as building blocks for the creation of thickness-controllable multilayer thin films in a layer-by-layer fashion, and also been used as flocculants or stabilizer of colloids. This paper reports novel finding that a kind of polyelectrolyte, polyamines, can facilely induce HAuCl4 to spontaneously form well-stabilized gold nanoparticles without the additional step of introducing a reducing reagent during the elevation of temperature, even at room temperature in some cases. The polymer chain-confined microenvironment and the acid-induced evolution of amide of such kind of polyelectrolyte solution play an important role in the nucleation and growth of gold nanoparticles. This method would not only be helpful to gain an insight into the formation of gold nanoparticles in polyelectrolyte systems, but also provide a novel and facile one-step polyelectrolyte-based synthetic route to polyelectrolyte protected gold nanoparticles in aqueous media for potential applications. More importantly, this strategy will be general to the preparation of other nanoparticles.

Preparation of gold nanoparticles protected with polyelectrolyte

Gold nanoparticles were synthesized through the reduction of tetrachlorauric acid (HAuCl4) by NaBH4, with polyethyleneimine(PEI) as stabilizer. The nanoparticles were characterized by LTV-vis spectroscopy and atomic. force microscopy(AFM).

In situ controllable synthesis of polyoxometalate nanoparticles in polyelectrolyte multilayers

Size-controlled Ag3PW12O40 nanoparticles have been synthesized in situ in polyelectrolyte multilayer thin films via layer-by-layer self-assembly.

Photoluminescent organic-inorganic composite films layer-by-layer self-assembled from the rare-earth-containing polyoxometalate Na-9[EuW10O36] and poly(allylamine hydrochloride)

Photoluminescent organic-inorganic composite films incorporating the rare-earth-containing polyoxometalate Na-9[EuW10O36] (EW) and poly(allylamine hydrochloride) (PAH) have been prepared by the layer-by-layer self-assembly method. UV-vis spectroscopy and ellipsometry were used to follow the fabrication process of the EW/PAH composite films. The experimental results show that the deposition process is linear and highly reproducible from layer to layer. An average EW/PAH bilayer thickness of ca. 2.1 nm was determined by ellipsometry. In addition, scanning electron microscopy and atomic force microscopy images of the EW/PAH composite films indicate that the film surface is relatively uniform and smooth. The photoluminescent properties of these films were investigated by fluorescence spectroscopy.

Ultrathin multilayer films incorporating Keggin-type heteropolyanion clusters

Two new ultrathin multiplayer films have been successfully prepared fi-om Keggin-type heteropoly acids H-4[SiW12O40] and H-3[PMo12O40] with polyelectrolytes PEI, PSS, and PAH, using the electrostatic layer-by-layer self-assembly, technique. The XR results reveal their film thickness at nanoscale (similar to 20 nm). According to the AFM images, it is believed that the surface roughness (rough degree of film surface) of the polyelectrolyte-polyoxometalate film greatly depends on the kind of polyoxometalates.

Formation and characterization of heteropolyacid/polycation multilayer films on gold electrode

Ultrathin multilayer films of a polybasic lanthanide heteropoly tungstate-molybdate complex and a cationic polymer of quaternized poly(4-vinylpyridine) partially complexed with osmium bis(2,2'-bipyridine) have been fabricated on a gold electrode precoated with a cysteamine self-assembled monolayer. The multilayer films have been characterized by optical spectroscopy, small-angle X-ray diffraction, and electrochemical methods (cyclic voltammetry and electrochemical impedance). Especially, the electrochemical impedance spectroscopy is developed to monitor the layer deposition processes. It provides important information such as double-layer capacitance and charge-transfer resistance. All obtained results reveal regular film growth with each layer adsorption. (C) 2001 The Electrochemical Society.

Investigation of the Mechanical Properties of Thin Films by Nanoindentation, Considering the Effects of Thickness and Different Coating-Substrate Combinations

In order to further investigate nanoindentation data of film-substrate systems and to learn more about the mechanical properties of nanometer film-substrate systems, two kinds of films on different substrate systems have been tested with a systematic variation in film thickness and substrate characteristics. The two kinds of films are aluminum and tungsten, which have been sputtered on to glass and silicon substrates, respectively. Indentation experiments were performed with a Nano Indent XP II with indenter displacements typically about two times the nominal film thicknesses. The resulting data are analyzed in terms of load-displacement curves and various comparative parameters, such as hardness, Young's modulus, unloading stiffness and elastic recovery. Hardness and Young's modulus are investigated when the substrate effects are considered. The results show how the composite hardness and Young's modulus are different for different substrates, different films and different film thicknesses. An assumption of constant Young's modulus is used for the film-substrate system, in which the film and substrate have similar Young's moduli. Composite hardness obtained by the Joslin and Oliver method is compared with the directly measured hardness obtained by the Oliver and Pharr method.

Magnetron Sputtering Growth of InAs0.3Sb0.7 Films on (100) GaAs Substrates: Strong Effect of Growth Conditions on Film Structure

The growth of highly lattice-mismatched InAs0.3Sb0.7 films on (100) GaAs Substrates by magnetron Sputtering has been investigated and even epitaxial lnAs(0.3)Sb(0.7) films have been successfully obtained. A strong effect of the growth conditions on the film structure was observed, revealing that there was a growth mechanism transition from three-dimensional nucleation growth to epitaxial layer-by-layer growth mode when increasing the substrate temperature. A qualitative explanation for that transition was proposed and the critical conditions for the epitaxial layer-by-layer growth mode were also discussed.

Preparation And Tribology Studies of Alkyl Carboxylic Acid Monolayer Films on Pei-Coated Glass Substrate

首次在涂敷PEI的玻璃表面上制备了癸酸及全氟癸酸的单分子层膜。研究了成膜机理及摩擦特性。结果表明。脱水剂DCCD促进了癸酸或全氟癸酸与PEI酞胺化的反应。导致两种羧酸在PEI表面产生了靠化学键（酞胺键）连接的稳定的单分子层膜,摩擦、磨损实验表明。单分子层有机膜的摩擦特性受膜的组成、表面能及有序性和堆积密度的重要影响。表面能越低,有序性和堆积密度越高。摩擦系数越低。与碳氢化合物相比。碳氟化合物形成的有序膜具有更高的强度和抗磨性能。

Essential and Non-Essential Work of Fracture of PI/SiO2 Hybrid Thin Films

Essential work of fracture (EWF) analysis is used to study the effect of the silica doping level on fracture toughness of polyimide/silica (PI/SiO2) hybrid films. By using double-edge-notched-tension (DENT) specimens with different ligament lengths, it seems that the introduction of silica additive can improve the specific essential work of fracture (w (e) ) of PI thin films, but the specific non-essential work of fracture (beta w (p) ) will decease significantly as the silica doping level increasing from 1 to 5 wt.%, and even lower than that of neat PI. The failure process of the fracture is investigated with online scanning electron microscope (SEM) observation and the parameters of non-essential work of fracture, beta and w (p) , are calculated based on finite element (FE) method.