Metal-polymer composite films based on polyacrylonitrile and silver nanoparticles. Preparation and properties

The structures consisting of silver nanoparticles and polyacrylonitrile (PAN) are synthesized by the photopolymerization method yielding a homogeneous dispersion and a small size spread of nanoinclusions in PAN matrices, which is observed in images of transmission electron microscopy. The optical properties of the nanocomposites are studied to depend upon conditions of their obtaining. The minimum in the transmission spectra in a wavelength region of 430 nm, which is attributed to the surface plasmon resonance of silver nanoparticles, is found. The absorption peaks in the infrared range are observed at ∼820 and ∼1110 cm⁻¹ for the silver nitrate (AgNO₃) and the photoinitiator, respectively.     

Structure and optical properties of the silver/polyacrylonitrile nanocomposites

Small-angle X-ray scattering is used to prove the formation of silver nanoparticles with sizes of 5–11 nm in siver/polyacrylonitrile nanocomposites synthesized via photopolymerization of a mixture containing silver, acrylonitrile, and photoinitiator. Optical spectra of nanocomposites obtained under different conditions are studied. The absorption spectra exhibit maxima at wavelengths of 420–450 nm related to the surface plasmon resonance of silver nanoparticles. IR spectra of the nanocomposites prove the formation of polyacrylonitrile in the course of the photopolymerization of monomer. The formation of metal nanoimpurities in polymer matrix leads to an increase in the intensity of photoluminescence and Raman scattering of polyacrylonitrile.     

The effect of concentration on the thermo-optical properties of colloidal silver nanoparticles

The thermo-optical properties of colloidal silver nanoparticles (AgNPs) are investigated under a low power laser irradiation at 532 nm. Colloidal AgNPs are synthesized by nanosecond pulsed laser ablation of a pure silver plate in distilled water. The morphology and size of the AgNPs are determined by transmission electron microscopy. Closed Z-scan measurements reveal that nonlocal thermo-optic process is responsible for the nonlinear refractive index of colloid containing different concentrations of silver nanoparticles. The Z-scan behavior of the nanoparticle samples has been investigated based on a nonlocal thermo-optic process and it is shown that the aberrant thermal lens model is in excellent agreement with the experimental results. Z-scan measurement fits have allowed the values of nonlinear refractive index (n₂) and thermo-optic coefficients (dn/dt) to be determined at different concentrations of silver nanoparticles. Large enhancement factors were measured for values of n₂ and dn/dt of the colloids at higher silver nanoparticle volume fraction. Our results suggest that nonlocal thermal nonlinear processes will play an important role in the development of photonic applications involving metal nanoparticle colloids.     

In Situ Synthesis of Oil-Based Polymer/Silver Nanocomposites by Photoinduced Electron Transfer and Free Radical Polymerization Processes

In this study, in situ synthesis of oil-based polymer–silver nanocomposites was achieved by using photoinduced free radical polymerization processes in which silver nanoparticles were formed by electron transfer reaction. An oil-based macromonomer was prepared and then copolymerized with styrene in the presence of AgNO₃. Copolymerization was started with free radicals formed by photolysis of 2,2-dimethoxy-2-phenyl acetophenone and simultaneously silver nitrate was reduced to metallic silver in nanosize by electron transfer reaction. The amount of photoinitiator influenced the size of silver nanoparticles formed within the polymer films. Nanocomposite films were characterized by TEM and TGA analysis. The obtained polymer nanocomposite film was also examined in respect of surface coating material that would have an antibacterial effect against Gram-positive, Gram-negative and spore-forming bacteria. It was demonstrated that suitably coated nanocomposite samples exhibited an antibacterial effect against these bacteria.     

New nanocomposites containing metal nanoparticles, carbon nanotube and polymer

Metal-carbon nanotube-graft-polymer (MCNT-g-P) nanocomposites were synthesized and characterized successfully. In this work, multiwall carbon nanotubes (MWCNT) were opened using HNO₃/H₂SO₄ mixture and filled by metal nanoparticles such as silver nanoparticles through wet chemistry method. Then MWCNT containing metal nanoparticles were used as macroinitiator for ring opening polymerization of ε-caprolactone and MCNT-g-P nanocomposites were obtained. Length of grafted polymer arms onto the MWCNT was controlled using MWCNT/ε-caprolactone ratio. Structure and properties of nanocomposites were evaluated by TEM, DSC, TGA, and spectroscopy methods.     

Novel electrospun PAN�CPVC composite fibrous membranes as polymer electrolytes for polymer lithium-ion batteries

Composite fibrous membranes based on poly(acrylonitrile)(PAN)-poly(vinyl chloride)(PVC) have been prepared by electrospinning. The fibrous membranes are made up of fibers of 850- to 1,300-nm diameters. These fibers are stacked in layers to produce a fully interconnected pore structure. Polymer electrolytes were prepared by immersing the fibrous membranes in 1 M LiClO₄-PC solution for 60 min. The condition of pure PAN polymer electrolytes is jelly, which has poor mechanical performance and cannot be used. But when PVC with a good mechanical stiffener was added to PAN, the condition of composite PAN?CPVC polymer electrolytes becomes free-standing. In addition, the optimum electrochemical properties have been observed for the polymer electrolyte based on PAN?CPVC (8:2, w/w) to show ionic conductivity of 1.05?×?10^?3 S cm^?1 at 25 °C, anodic stability up to 4.9 V versus Li/Li⁺, and a good compatibility with lithium metal resulting in low interfacial resistance. The promising results showed that fibrous PEs based on PAN?CPVC (8:2, w/w) have good mechanical stability and electrochemical properties. This shows a great potential application in polymer lithium-ion batteries.     

Preparation and properties of nano-sized Ag and Ag2S particles in biopolymer matrix

Silver (Ag) and silver sulfide (Ag₂S) nanoparticles were synthesized in a sago starch matrix. The resulting nanocomposites were investigated using structural, optical and thermal methods. XRD spectra of the nanocomposites confirmed the presence of nanostructured silver (cubic phase) and silver sulfide (monoclinic phase) in the matrix. TEM micrographs showed that the nanoparticles are mostly spherical in shape. Analyzes of the optical properties of the silver nanocomposite aqueous dispersions/solutions of various concentrations were carried out. The results and the theoretical considerations suggested that at high concentrations there is a release of silver nanoparticles from the composite in the water environment. Further dilution produces homogeneous solution in which silver nanoparticles are capped with starch macromolecules. TGA analysis revealed reduced thermal stability of the nanocomposites with respect to pure starch matrix.     

Characterization and antimicrobial activity of silver nanoparticles prepared by a thermal decomposition technique

Recently, there has been an increasing need of efficient synthetic protocols using eco-friendly conditions including low costs and green chemicals for production of metal nanoparticles. In this work, silver nanoparticles (silver NPs) with average particle size about 10 nm were synthesized by using a thermal decomposition technique. Unlike the colloidal chemistry method, the thermal decomposition method developed has advantages such as the high crystallinity, single-reaction synthesis, and easy dispersion ability of the synthesized NPs in organic solvents. In a modified synthesis process, we used sodium oleate as a capping agent to modify the surface of silver NPs because the oleate has a C₁₈ tail with a double bond in the middle, therefore, forming a kink which is to be effective for aggregative stability. Importantly, the as-synthesized silver NPs have demonstrated strong antimicrobial effects against various bacteria and fungi strains. Electron microscopic studies reveal physical insights into the interaction and bactericidal mechanism between the prepared silver NPs and tested bacteria in question. The observed excellent antibacterial and antifungal activity of the silver NPs make them ideal for disinfection and biomedicine applications.     

A novel method of nanocrystal fabrication based on laser ablation in liquid environment

Metal nanoparticles can be prepared by a novel technique that consists of the laser ablation of a solid target immersed in a water solution of a metal salt. Silicon was chosen as the most adequate target to synthesize silver and gold nanoparticles from a water solution of either AgNO₃ or HAuCl₄. The influence of both the silver nitrate concentrations and the irradiation time of the Si target on the optical properties of the Au and Ag nanoparticles have been investigated. The crystalline nature of the metal nanoparticles has been determined by X-ray diffraction (XRD). Average size and particle size distribution have been measured by means of TEM. The absorbance spectra show the characteristic band of the surface resonant plasmon of silver and gold nanoparticles.     

Fluorescence Modulation of Acridine and Coumarin Dyes by Silver Nanoparticles

Silver nanoparticles were synthesized by chemical reduction of silver ions by sodium borohydride in the presence of poly-(N)-vinyl-2-pyrrolidone in solution of short chain alcohols. The nanoparticles are stable in 2-propanol, and the average diameter of the Ag colloid obtained in this solvent is about 6 nm. The photophysical properties of acridinium and coumarin dyes in 2-propanol are affected by the presence of silver nanoparticles. The interaction of silver nanoparticles with acridinium derivative leads to a spectral change of its intramolecular charge transfer (ICT) absorption band. The dye emission increases suddenly with the initial addition of the Ag metal nanoparticles, but at a high concentration of the colloid, static fluorescence quenching occurs with a progressive decrease of the fluorescence efficiency. Amino coumarin fluorescence is only quenched by the silver nanoparticles in solution.     

Laser-induced growth and reformation of gold and silver nanoparticles

The sizes, shapes, and growth rates of gold and silver nanoparticles stabilized with polyvinylpyrrolidone in water can be controlled by using picosecond laser pulses. The nucleation of small metal clusters formed with NaBH₄ addition to produce nanoparticles takes two months with aging but 30 min with laser irradiation. Laser pulses can also induce nanoparticles to have narrow size and shape distribution or to undergo aggregation into much larger particles. The latter process is more likely found when the metal is silver or the irradiation wavelength is short. Laser-induced growth and shape transformation processes are explained in terms of BH₄ ⁻ depletion, metal fusion, and electron ejection followed by disintegration.     

Facile shape control synthesis and optical properties of silver nanoparticles stabilized by Daxad 19 surfactant

It is known that silver (Ag) nanoparticles are attractive due to their novel and mild chemical and physical properties. In this research, anisotropic mono-dispersed silver nanoparticles are synthesized via a simple chemical reduction method and assisted by Daxad 19 surfactant. The reactant temperatures and weight ratios of the chemical constituents play a key role in controlling the hybrid shaping mechanism. The results indicate that the reduction rate of Ag⁺ to Ag⁰ nanoparticles is enhanced significantly with increasing weight ratios of Daxad 19 and AgNO₃ under controlled reactant temperature. The results show that the as-prepared silver nanoparticles are well-dispersed and uniform in size and shape. The dimensions of the particles are easily controlled. A comparison between experimental absorbance UV-visible spectra and simulated spectra from Mie's Scattering Theory is carried out. It is observed that the simulated spectrum confirms well with the optical behaviour of the experimental spectra.     

Ion synthesis of silver nanoparticles in viscous-fluid epoxy resin

A method is described for the ion synthesis of silver nanoparticles in epoxy resin that is in a viscousfluid state (viscosity 30 Pa s) during irradiation. The viscous-fluid or glassy polymer is implanted by 30-keV silver ions at a current density of 4 μA/cm² in the ion beam in the dose range 2.2 × 10¹⁶–7.5 × 10¹⁶ ions/cm². The epoxy layers thus synthesized contain silver nanoparticles, which are studied by transmission electron microscopy and optical absorption spectroscopy. The use of the viscous-fluid state increases the diffusion coefficient of the implanted impurity, which stimulates the nucleation and growth of nanoparticles at low implantation doses and allows a high factor of filling of the polymer with the metal to be achieved.     

Fabrication of silver nanoparticles deposited on boehmite sol for surface enhanced Raman scattering

The composite consisting of silver nanoparticles deposited on boehmite hybrid was synthesized by NaBH₄ reduction technique. The morphology of the composite was studied by TEM, UV/Vis spectrophotometer and particle sizer. The size of the silver nanoparticles deposited on the surface of the boehmite ranged from 10 nm to 100 nm. The contact of silver nanoparticles increased by means of deposition of silver nanoparticles on the boehmite sol and the aggregation of the composites. This leads to the appearance of a shoulder at 450 nm in the UV-Vis absorption spectra with the addition of 0.15 mg and 1.5 mg boehmite. It was found that the intensity of the SERS in the case of the composite was higher than for silver colloids consisting of a concentration of silver greater than 3.2 mM.     

Formation of silver nanoparticles during deposition onto viscous-fluid epoxy resin

A new method is proposed for synthesizing metallic nanoparticles in a polymer matrix. These nanoparticles are synthesized during thermal vacuum evaporation of a metal (4.8 × 10⁻⁶ g/cm²) onto the surface of viscousfluid epoxy resin (at a viscosity of 20–120 Pa s) having room temperature, which is well below the glass transition temperature of the polymer. As a result, epoxy resin layers containing silver nanoparticles in their volume form; these nanoparticles are studied by transmission electron microscopy and optical absorption spectroscopy. Various types of disperse structures formed by metallic nanoparticles in the polymer are detected. The morphology of the composite material is found to be controlled by the polymer viscosity and the metal deposition time.     

Methoxycarbonyl-terminated hyperbranched poly(amine-ester) as templates for synthesis of silver nanoparticles

Highly stable and spherical silver nanoparticles, stabilized by methoxycarbonyl-terminated hyperbranched poly(amine-ester) (HPAE-COOCH₃), were synthesized in water with reducing AgNO₃/HPAE-COOCH₃ using two methods, viz. NaBH₄ and ultraviolet irradiation. HPAE-COOCH₃ was found to play a key role in the formation of nanoparticles. UV–visible absorption, Transmission electron microscopic (TEM), and Fourier transform infrared spectroscopy (FT-IR) had been used to study the structure and characterization of the silver nanoparticles. The absorption peaks of the silver nanoparticles appear at ~420 nm in UV–visible absorption spectra; average particle size reduced by NaBH₄ is ~30 nm, which is ~10 and ~15 nm, respectively, when ultraviolet irradiation time is 12 and 24 h. FT-IR spectra confirm that there is strong interaction between silver nanoparticles and HPAE-COOCH₃. And silver nanoparticles/HPAE-COOCH₃ aqueous solution can keep stable for more than 3 months.     

Fusarium solani: a novel biological agent for the extracellular synthesis of silver nanoparticles

We report extracellular biosynthesis of silver nanoparticles by Fusarium solani (USM-3799), a phytopathogen causing disease in onion, when challenged with 1 mM silver nitrate (AgNO₃). The formation of nanoparticles was characterized by visual observation followed by UV–Vis spectrophotometric analysis, which showed a peak at about 420 nm, which is very specific for silver nanoparticles. Further analysis carried out by Fourier Transform Infrared Spectroscopy (FTIR), provides evidence for the presence of proteins as capping agent, which helps in increasing the stability of the synthesized silver nanoparticles. Transmission Electron Microscopy (TEM) investigations confirmed that silver nanoparticles were formed. The synthesized silver nanoparticles were found to be polydispersed, spherical in the range of 5–35 nm with average diameter of 16.23 nm. Extracellular synthesis of nanoparticles could be highly advantageous from the point of view of synthesis in large quantities and easy downstream processing.     

Enhancement of photoluminescence of the CdSe/CdS quantum dots on quartz substrates in the presence of silver nanoparticles

Multilayer systems consisting of layers of hybrid quantum dots are fabricated. The quantum dots with the CdSe/CdS core/shell structure are chemically synthesized and deposited on the surface of quartz glass that contains ion-synthesized silver nanoparticles in the near-surface region. Silver nanoparticles exhibit optical absorption owing to the localized surface plasmon resonance. Variations in the photoluminescence intensity of the layer related to an increase in the distance from the quartz surface with metal nanoparticles are studied. An increase in the photoluminescence intensity is observed under excitation in the spectral region of the plasmon absorption of silver nanoparticles. An optimal distance between the layers is determined to maximize the enhancement of the photoluminescence of quantum dots in the presence of the near field of metal nanoparticles.     

UV-protection properties of electrospun polyacrylonitrile nanofibrous mats embedded with MgO and Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles

This article describes the ultraviolet (UV) protection of MgO and Al₂O₃ nanoparticles embedded electrospun polyacrylonitrile (PAN) nanofibrous mats. UV radiation is a harmful part of sunlight and prolonged exposure to it can cause serious skin damages. In this research, nanofibrous mats consisting of nanofibers with different diameters containing different amounts of MgO, Al₂O₃, MgO Plus, and Al₂O₃ Plus nanoparticles were produced, and their UV-protection was measured. The specific surface area of MgO, MgO Plus, Al₂O₃, and Al₂O₃ Plus nanoparticles was 230, 600, 275, and 550 m²/g, respectively. The mean diameter of electrospun PAN nanofibers embedded with metal oxide nanoparticles was in the range of 665–337 nm. The results showed that the UV-protection (shielding) capability of the mats strongly depends on fiber diameter; in fact a thin mat of nanofibers has a much stronger UV-protection in comparison to a thicker mat composed of regular fibers. UV transmission is reduced as a result of embedding MgO and Al₂O₃ nanoparticles in the electrospun PAN nanofibrous mats. MgO Plus and Al₂O₃ Plus show higher UV-protection than MgO and Al₂O₃.     

The effect of the deposition parameters on size, distribution and antimicrobial properties of photoinduced silver nanoparticles on titania coatings

Controlled photodeposition of silver nanoparticles (AgNP) on titania coatings using two different sources of UV light is described. Titania (anatase) thin films were prepared by the sol-gel dip-coating method on silicon wafers. AgNPs were grown on the titania surface as a result of UV illumination of titania films immersed in aqueous solutions of silver nitrate. UV xenon lamp or excimer laser, both operating at the wavelength 351 ± 5 nm, was used as illumination sources. The AFM topography of AgNP/TiO₂ nanocomposites revealed that silver nanoparticles could be synthesized by both sources of illumination, however the photocatalysis carried out by UV light from xenon lamp illumination leads to larger AgNP than those synthesized using the laser beam. It was found that the increasing concentration of silver ions in the initial solution increases the number of Ag nanoparticles on the titania surface, while longer time of irradiation results the growth of larger size nanoparticles. Antibacterial tests performed on TiO₂ covered by Ag nanoparticles revealed that increasing density of nanoparticles enhances the inhibition of bacterial growth. It was also found that antibacterial activity drops by only 10-15% after 6 cycles compared to the initial use.