Double stabilization of silver molecular clusters in thin films

The evolution of spectral and luminescent properties of Ag-containing composite coatings prepared by liquid technique has been studied. Double stabilization allows forming thin oxide films containing luminescent small Ag_n (n?<?5) molecular clusters using the liquid technique. These clusters are non-stable intermediate products during the formation of Ag nanoparticles from the ions and neutral atoms. It was found that small luminescent Ag_n molecular clusters (n?<?5) formed in the solutions at the presence of polyvinylpyrrolidone (PVP) remain in PVP/metal nitrates composite coatings and in the calcined metal oxide coatings. Spatial separation of small Ag molecular clusters in the coatings by the oxide nanoparticles of ZnO and MgO prohibits silver clusters growth and non-luminescent silver nanoparticles formation and allows saving coatings’ luminescence properties during thermal treatment.

     

Poly(methyl methacrylate) composites with size‐selected silver nanoparticles fabricated using cluster beam technique

An embedment of metal nanoparticles of well‐defined sizes in thin polymer films is of significant interest for a number of practical applications, in particular, for preparing materials with tunable plasmonic properties. In this article, we present a fabrication route for metal–polymer composites based on cluster beam technique allowing the formation of monocrystalline size‐selected silver nanoparticles with a ±5–7% precision of diameter and controllable embedment into poly (methyl methacrylate). It is shown that the soft‐landed silver clusters preserve almost spherical shape with a slight tendency to flattening upon impact. By controlling the polymer hardness (from viscous to soft state) prior the cluster deposition and annealing conditions after the deposition the degree of immersion of the nanoparticles into polymer can be tuned, thus, making it possible to create composites with either particles partly or fully embedded into the film. Good size selection and rather homogeneous dispersion of nanoparticles in the thin polymer film lead to excellent plasmonic properties characterized by the narrow band and high quality factor of localized surface plasmon resonance. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1152–1159     

Ag nanoparticles deposited onto silica,titania, and zirconia mesoporous films synthesized by sol–gel template method

A variety of Ag nanoparticles/oxide mesoporous films with templated silica, titania, and zirconia was synthesized by sol–gel method at glass, aluminum, and silicon substrates using metal alkoxides (tetraethoxysilane, titanium tetraisopropoxide, and zirconium tetrapropoxide) and AgNO₃ as precursors of oxide films and Ag nanoparticles, respectively, and Pluronic P123 as a template agent. Oxide films alone and Ag/oxide composites were characterized using hexane adsorption, X-ray diffraction (XRD), Raman and ultraviolet (UV)/vis spectroscopies, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) methods. The distribution of Ag nanoparticles within the films, their sizes, intensity, and position of surface plasmon resonance (SPR) absorbance band at λ = 400 nm, as well as the textural and structural characteristics of whole films depend on treatment temperature, types of substrates and oxide matrices, oxide crystallization, and Ag content. Ag nanoparticles form preferably on the outer surface of the films under lower sintering temperatures if the amount of loaded silver is low. Oxide crystallization (e.g., TiO₂) promotes silver embedding into the outer film layer. At higher silver content (≥10 at.%) and higher calcination temperature (873 K), silver nanoparticles could be entrapped more uniformly along the film profile because of more intensive evaporation of silver droplets from the outer surface of the films on heating.     

Silicone composites containing stabilized silver clusters or nanoparticles

Silver nanoparticles are of high importance due to their electrical, magnetic, and optical properties, as well as catalytic and biocidal activity that are superior to the bulk silver and other metals. To prepare certain devices, generally, silver is incorporated into a matrix either as preformed or in situ‐generated particles. Silver nanoparticles were generated in situ into a silicone matrix formed by cohydrolysis of the mixture of silanes, each of them having a certain role: dimethyldiethoxysilane (DMDES) as a precursor for highly flexible polydimethylsiloxane, methyltriethoxysilane (MTES) as a cross‐linker highly compatible with polydimethylsiloxane, and 3‐aminopropyltriethoxysilane as a stabilizer, since it can readily complex to silver atoms through its amine functionality. Dimethylformamide (DMF) was used as a solvent for the silver nitrate and reducing agent. The samples were investigated both in sol state and as aged coating films deposited on glass substrate. The complexation of the silver and the matrix formation were emphasized by FTIR. The size of the formed silicone particles encapsulating silver was estimated by dynamic light scattering (DLS) (about 100 nm) in sol and by AFM in film (about 90 nm). The formation of the clusters or nanoparticles depending on the ratio between the reducing and complexing agents was evidenced by UV–Vis absorption spectra. Thus, it would create conditions to stop and isolate clusters at the desired size by precise control of the experimental conditions. The composites could be used alone as antibacterial‐coating materials but also, porous silica having incorporated silver clusters with potential applicability in catalysis may result after their calcination. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis of Silver and Gold Nanoparticles by a Novel Electrochemical Method

Spherical silver and gold nanoparticles with narrow size distributions were conveniently synthesized in aqueous solution by a novel electrochemical method. The technological keys to the electrochemical synthesis of monodispersed metallic nanoparticles lie in the choice of an ideal stabilizer for the metallic nanoclusters and the use of a rotating platinum cathode. Poly(N‐vinylpyrrolidone) (PVP) was chosen as the stabilizer for the silver and gold clusters. PVP not only protects metallic particles from agglomeration, but also promotes metal nucleation, which tends to produce small metal particles. Using a rotating platinum cathode effectively solves the technological difficulty of rapidly transferring the (electrochemically synthesized) metallic nanoparticles from the cathode vicinity to the bulk solution, avoiding the occurrence of flocculates in the vicinity of the cathode, and ensuring the monodispersity of the particles. The particle size and particle size distribution of the silver and gold nanoparticles were improved by adding sodium dodecyl benzene sulfonate (SDBS) to the electrolyte. The electrochemically synthesized nanoparticles were characterized by TEM and UV/Vis spectroscopy.     

Preparation and resistivity study of silver nanocomposite films using spin‐assisted layer‐by‐layer assembly

Nanocomposite films [Ag/(PAH‐PSS)_nPAH]_m were fabricated on a silicon substrate using a time‐ and cost‐efficient spin‐assisted layer‐by‐layer (SA‐LbL) self‐assembly technique. A virtually monolayer‐like layer of self‐assembled silver nanoparticles was formed when deposition time increased to 30 min. It was found that polymer multilayers could effectively decrease the resistivity of silver nanoparticle monolayer, which was far higher than that of bulk silver metal; however, the resistivity of Ag/(PAH‐PSS)_nPAH multilayer films increased along with the increasing of the number of polymer bilayers. XPS investigations showed that silver nanoparticles were partially oxidized, which might be the major cause of the high resistivity of silver nanoparticle monolayer. Copyright © 2008 John Wiley & Sons, Ltd.     

Dependence of Property of Silver Nanoparticles within Dendrimer-template on Molar Ratios of Ag+ to PAMAM Dendrimers

G5.0‐OH PAMAM dendrimers were used to prepare fluorescent silver clusters with weaker ultraviolet irradiation reduction method, in which the molar ratio of Ag⁺ to PAMAM dendrimers was the key factor to determine the geometry and properties of silver nanoparticles. The results showed that because of G5.0‐OH PAMAM dendrimers as strong encapsulatores, when the molar ratios of Ag⁺ to PAMAM dendrimers was smaller than 5, the obtained Ag_n clusters (n<5) had line structures and "molecular‐like" properties, which were highly fluorescent and quite stable in aqueous solution. Whereas when the molar ratios were between 5 and 8, the obtained Ag_n clusters were 2D structures and their fluorescence was weaker. When the molar ratio was larger than 8, the structure of silver nanoparticles was 3D and no fluorescence was observed from the obtained silver nanoparticles.     

Chitosan aerogel containing silver nanoparticles: From metal-chitosan powder to porous material

The work presents a synthetic approach that combines methods of metal vapor synthesis (MVS), gelation and supercritical drying in order to obtain chitosan aerogels containing silver nanoparticles. On the first stage, two types of silver organosols were prepared via the eco-sustainable MVS method. Then the prepared silver organosols were used to modify chitosan powders for producing metal-chitosan powder composites. Gelation of the powder composites was performed in oxalic acid at elevated temperatures. Supercritical drying of the gels was implemented in order to preserve the formed porous structures. Thus, the chitosan powders modified with MVS-produced silver nanoparticles were used to prepare metal-chitosan aerogels. Characterization of the structure and the morphology of both powder and aerogel silver-chitosan composites was conducted by means of low temperature nitrogen adsorption, X-ray photoelectron spectroscopy, X-ray powder diffraction, small-angle X-ray scattering, SEM and TEM. Changes in the structure and morphology of silver nanoparticles between powder and aerogel composites were analyzed.     

In situ generation of silver nanoparticles in cellulose matrix using Azadirachta indica leaf extract as a reducing agent

In the present work, silver nanoparticles (AgNPs) were in situ generated in cellulose matrix using leaf extract of Azadirachta indica as a reducing agent. The cellulose/AgNP composite films prepared were characterized by FTIR, X-ray diffraction (XRD), scanning electron microscope, and antibacterial tests. The infrared spectra indicated the association of organic materials with silver nanoparticles to serve as capping agents. Scanning electron micrographs showed that synthesized silver nanoparticles were nearly uniform and spherical in shape with diameter in the range of 61–110?nm. XRD confirmed the formation of AgNPs and Ag–O nanoparticles. The nanocomposite films showed good antibacterial activity against Escherichia coli bacteria.     

Metal nanocomposite films prepared in situ from PVA and silver nitrate. Study of the nanostructuration process and morphology as a function of the in situ routes

Cast‐hybrid films composed of polyvinyl alcohol (PVA) and silver nitrate were treated according to three different ways, thermal annealing, UV‐irradiation, and chemical reduction by a borohydride solution, to obtain PVA/silver nanocomposite films. The nanostructuration process was studied as a function of the treatment conditions, and discussed as a function of the mobility state of the polymer chains in the nanocomposite matrix during treatment. A homogeneous dispersion of crystalline silver nanoparticles was obtained by thermal annealing above T_g and below T_m and UV‐lamp irradiation below T_g. For these two treatments, the major processing parameters were the annealing temperature and time and the UV‐exposure time, respectively. For low‐conversion rate in Ag(0), the films evolved upon ageing at room temperature. Totally different morphology and Ag(0) conversion were achieved by chemical reduction in a borohydride solution. All the silver ions were reduced into Ag(0), and crystalline silver nanoparticles layers parallel to the film surface were observed after the treatment. This morphology was related to the high‐swollen state of the polymer matrix during treatment. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2062–2071, 2008     

A green approach to prepare Ag NPs loaded IC/PVA polymeric film for antimicrobial applications

In this study, glyoxal-cross-linked Iota carrageenan (IC) /poly(vinyl alcohol) PVA films were prepared and loaded with silver nanoparticles via a green approach, consisting of sweet lime juice induced in-situ reduction of Ag(I) ions to nano silver within the film matrix. The formation of silver nanoparticles was confirmed using UV–visible spectrophotometry. The Ag NPs-loaded films were also characterized by X-ray diffraction (XRD), Scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR). The dynamic water uptake data were interpreted by the ‘Power functional model’. The films showed fair antimicrobial action against bacteria E. Coli.     

In situ formation of silver nanoparticles within an amphiphilic graft copolymer film

Silver nanoparticles were prepared by UV irradiation from silver salts, such as AgBF₄ or AgNO₃, when dissolved in an amphiphilic film of poly((oxyethylene)₉ methacrylate)‐graft‐poly((dimethyl siloxane)_n methacrylate), POEM‐g‐mPDMS. The in situ formation of silver nanoparticles in the graft copolymer film was confirmed by transmission electron microscopy (TEM), UV‐visible spectroscopy, and wide angle X‐ray scattering (WAXS). The results demonstrated that the use of AgBF₄ yielded silver nanoparticles with a smaller size (～5 nm) and narrower particle distribution when compared with AgNO₃. The formation of silver nanoparticles was explained in terms of the interaction strength of the silver ions with the ether oxygens of POEM, as revealed by differential scanning calorimetry (DSC) and X‐ray photoelectron spectroscopy (XPS). It was thus concluded that a stronger interaction of silver ions with the ether oxygens results in a more stable formation of silver nanoparticles, which produces uniform and small‐sized nanoparticles. DSC and small angle X‐ray scattering (SAXS) data also showed the selective incorporation and in situ reduction of the silver ions within the hydrophilic POEM domains. Excellent mechanical properties of the nanocomposite films (3–5 × 10⁵ dyn/cm²) were observed, mostly because of the confinement of silver nanoparticles in the POEM chains as well as interfaces created by the microphase separation of the graft copolymer film. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1283–1290, 2007     

Methyltriethoxysilane-derived sol-gel coatings doped with silver metal particles

Silica sol-gel films were prepared by dipping, starting from an acid catalyzed solution of methyltriethoxysilane (MTES) and tetraethoxysilane (TEOS). Silver metal nanoparticles were produced in the silica layer by introducing in the sol-gel precursor solution AgNO₃ or AgClO₄·H₂O. The silver ions were thermally reduced in air at 800°C, giving an intense yellow coating film. The silver metal particles were observed by transmission electron microscopy and X-ray diffraction. The diameter of the silver particles was found to be about 10 nm. Absorption measurements in the UV-Vis were used to evaluate the volume fraction of silver colloids embedded in the silica layer.     

Preparation and properties of cellulose/silver nanoparticle composites with in situ-generated silver nanoparticles using Ocimum sanctum leaf extract

In the present work, silver nanoparticles were in situ-generated in cellulose matrix using Ocimum sanctum leaf extract as a reducing agent. Regenerated wet cellulose films were first immersed in O. sanctum leaf extract and then it was allowed to diffuse into the films. The leaf extract–diffused wet films were dipped in different concentrated aq.AgNO₃ solutions. The leaf extract inside the wet films reduced AgNO₃ into nanosilver. The dry composite films were black in color. Some of the nanoparticles were also formed outside the film in the solution. The nanoparticles were viewed by transmission electron microscopy and scanning electronic microscopy techniques. The composite films showed good antibacterial activity. The cellulose, matrix, and the composite films were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, and thermogravimetric analysis techniques. The tensile properties of the composite films were higher than those of the matrix. These biodegradable films can be used for packaging and medical purposes.     

Synthesis of silver and copper nanoparticle containing a-C:Hby ion irradiation of polymers

One of the many applications of diamond like carbon (DLC) is the biocompatible coating of medical tools and implants. The most recent field of interest concerns the generation of antimicrobial activity in combination with the excellent wear resistance and biocompatibility of DLC. As has already been shown for polymers, nanoparticles of silver or copper within a carbonacious matrix have a bactericidal effect.In this work we describe a new technique to produce amorphous hydrogenated carbon films (a-C:H), which contain nanometer sized clusters of silver or copper. The hybrid deposition process is based on sol–gel synthesis of polymer films and subsequent ion-induced densification and cross-linking to form a-C:H. By thermal or UV-induced reduction of metal salts in polymer solution, colloidal metal particles are produced. In this way polymer films, already containing noble metal nanoclusters, can be deposited in a wet chemical step. Upon sol–gel deposition, the polymer is subjected to ion irradiation. Based on earlier results, the influence of ion energy on chemical and mechanical properties, as well as bonding structure is investigated. Special attention is also dedicated to ion-induced diffusion and growth as well as oxidation effects.     

Preparation of polyimide/BaTiO3/Ag nanocomposite films via in situ technique and study of their dielectric behavior

Triphase polyimide nanocomposite films were fabricated using barium titanate （BaTiO3） with high dielectric constant and silver （Ag） with high conductivity as fillers. In situ method was utilized to obtain the homogeneous dispersion of nanoparticles. The in situ polymerization of polyimide precursor-poly（amic acid） was performed in the presence of BaTiO3 particles. Silver compound 1,1,1-trifluoro-2,4-pentadionato silver（I） was added into the BaTiO3 containing poly（amic acid） solution to achieve silver nanoparticles via in situ self metallization technique. The thermally induced reduction converted silver （I） to metallic silver with concomitant imidization of poly（amic acid） to polyimide. Both BaTiO3 and silver nanoparticles were uniformly dispersed in the polyimide substrate. The dependence of dielectric behavior on the BaTiO3 and Ag contents was studied. The incorporation of small amount of silver nanoparticles greatly increased dielectric constant of composite films.     

Synthesis and characterization of novel four-arm star PDMAEMA-stabilized colloidal silver nanoparticles

Spontaneous formation and efficient stabilization of colloidal silver nanoparticles were achieved in aqueous four-arm star poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) solution at ambient temperature in the absence of any other reducing agent. In this reaction, four-arm star PDMAEMA acted as both reducing and stabilizing agents for silver nanoparticles. More importantly, four-arm star PDMAEMA is a tertiary-amine-containing star homopolymer, which shows that the scope of the reducing and stabilizing agents for metal nanoparticles can be extended from the general homopolymers and the block copolymers to the water-soluble simple tertiary-amine-containing star homopolymers. Fourier transform infrared, UV–vis absorption spectroscopy, and transmission electron microscopy were used to characterize the synthetic silver nanoparticles. A plausible mechanism for the formation of silver nanoparticles was proposed in the presence of linear and star PDMAEMA homopolymers. Moreover, the size of the resultant silver nanoparticles can be easily tuned by changing the concentrations of AgNO₃.     

Preparation and Optical Properties of New Metal/Macromolecule Architectures

Polymer nanocomposite films with unusual and anisotropic optical properties were obtained by the controlled in-situ generation of noble metal nanoparticles (NPs). Poly(vinyl alcohol) (PVA) and poly(ethylene-co-vinylalcohol) (EVAl) nanocomposites containing gold and silver NPs were efficiently produced by a photo-reduction or thermal process both operating directly in the solid state and resulted efficiently stabilized by the presence of polymer hydroxyl groups, which prevent particles agglomeration. Uniaxial drawing of the NPs/polymer composites promoted anisotropic packing of the embedded particles along the stretching direction of the film, resulting in a shift of the surface plasmon resonance well above 40 nm and thus producing a well-defined polarization-dependent colour change. Such nanostructured materials when are obtained in the form of thin films can be applied to several fields, from sensor to photonics (i.e., macromolecular strain sensor, linear absorbing polarizer).     

Directed Self‐Assembly of Diblock Copolymer Thin Films on Prepatterned Metal Nanoarrays

The sequential layer by layer self‐assembly of block copolymer (BCP) nanopatterns is an effective approach to construct 3D nanostructures. Here large‐scale highly ordered metal nano­arrays prepared from solvent annealed thin films of polystyrene‐block‐poly(2‐vinylpyridine) (PS‐b‐P2VP) diblock copolymer are used to direct the assembly of the same BCP. The influence of initial loading concentration of metal precursor, the type of metal nanoparticle (gold, platinum, and silver), and the nanoparticle–substrate interaction on the directed assembly behavior of the upper BCP layer have been focused. It is found that the upper BCP film can be completely directed by the gold nanoarray with P2VP domain exclusively located between two adjacent gold nanowires or nanodots, which behaves the same way as on the platinum nanoarray. While the silver nanoarray can be destroyed during the upper BCP self‐assembly with the silver nanoparticles assembled into the P2VP domain. Based on the discussions of the surface energy of nanoparticles and the interplay between nanoparticle–substrate interaction and nanoparticle–polymer interaction, it is concluded that the effect of immobilization of nanoparticles on the substrate, together with entropy effect to minimize the energetically unfavorable chain stretching contributes to the most effective alignment between each layer.

     

High temperature nucleation and growth of glutathione protected ~Ag75 clusters

We report the first high temperature solution state synthesis of glutathione (-SG) protected atomically precise silver clusters. Noble metal cluster synthesis from metal ions generally requires ice cold temperatures as they are extremely sensitive and high temperature routes are used only for core reduction methods, starting from nanoparticles. The clusters formed by the new route have distinct features in their absorption profile and they exhibit red luminescence. They are characterised by other spectroscopic and microscopic techniques and a tentative formula of Ag(75)(SG)(40) has been assigned.