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.     

Gold nanoparticles produced by laser ablation in water and in graphene oxide suspension

The comparison between two different approaches based on the use of the laser ablation in medium to synthetise gold nanoparticles is presented and discussed. Deionised water as well as a graphene oxide (GO) suspension in deionised water have been employed as solution to produce gold nanoparticles by laser ablation. In the former case, the nanoparticles assembly has been stabilised by using surfactants, but in the latter case to avoid undesired effects the use of chemicals was not necessary and Au reduced graphene oxide (Au-rGO) nanocomposites have been obtained. The structure, size and composition of the gold nanoparticles and of the Au–rGO nanocomposites have been monitored by UV–Vis–NIR absorption spectroscopy and Raman spectroscopy, the transmission and scanning electron microscopies and the X-ray energy-dispersive spectroscopy. The presented methodology of Au rGO nanocomposites preparation could represent a green alternative on the production of metallic nanoparticles in biocompatible environment.     

Ligand-free gold–silver nanoparticle alloy polymer composites generated by picosecond laser ablation in liquid monomer

Polymer matrix nanocomposites filled with metallic and alloy nanoparticles add functionality in various applications such as optical devices and in the energy sector. However, matrix coupling agents or nanoparticle ligands may be unwanted additives, potentially inhibiting the resulting nanocomposite to be processed by injection molding. The generation of stabilizer-free Au, Ag, and AuAg alloy nanoparticle acrylate composites is achieved by picosecond-pulsed laser ablation of the respective metal target in the liquid monomer. Complementary to laser ablation of the solid alloy, we have alloyed nanoparticles by post-irradiation of Au and Ag colloids in the liquid monomer. The optical properties of the colloidal nanoparticles are successfully transferred to the solid poly(methyl methacrylate) matrix and characterized by their plasmon resonance that can be easily tuned between 400 and 600 nm by laser alloying in the liquid monomer.     

Photoluminescent zinc oxide polymer nanocomposites fabricated using picosecond laser ablation in an organic solvent

Nanocomposites made of ZnO nanoparticles dispersed in thermoplastic polyurethane were synthesized using picosecond laser ablation of zinc in a polymer-doped solution of tetrahydrofuran. The pre-added polymer stabilizes the ZnO nanoparticles in situ during laser ablation by forming a polymer shell around the nanoparticles. This close-contact polymer shell has a layer thickness up to 30 nm. Analysis of ZnO polyurethane nanocomposites using optical spectroscopy, high resolution transmission electron microscopy and X-ray diffraction revealed that oxidized and crystalline ZnO nanoparticles were produced. Those nanocomposites showed a green photoluminescence emission centred at 538 nm after excitation at 350 nm, which should be attributed to oxygen defects generated during the laser formation mechanism of the monocrystalline nanoparticles. Further, the influence of pulse energy and polymer concentration on the production rate, laser fluence and energy-specific mass productivity was investigated.     

Tuning the microstructure of pulsed laser deposited polymer–metal nanocomposites

Pulsed laser deposition was used to grow complex polymer–metal nanocomposites consisting of Ag, Cu and Nb clusters embedded in a poly(methyl-methacrylate) (PMMA) matrix. During deposition at room temperature, the size and amount of the metal clusters can be tuned in different ways. First, it is controlled by the number of laser pulses hitting the respective targets. In the case of Ag, a bimodal size distribution of the clusters is observed, induced by total coalescence and secondary nucleation processes. For Cu and Nb, much smaller clusters and higher cluster densities are obtained due to a stronger reactivity with the polymer and thus a lower diffusivity in the PMMA. Additionally, the microstructure of the Ag clusters is affected by the degree of cross linking of the polymer and can be influenced by pre-deposition of nucleation seeds in the form of small Cu clusters. PACS 68.55.-a; 81.15.Fg; 82.35.Np     

Photoinduced nanocomposites—creation, modification, linear and nonlinear optical properties

UV irradiation of materials consisting of a polymer matrix that possesses precursors of noble metals followed by annealing results in creation of metal nanoparticles within the irradiated domains. Such photoinduced nanocomposites are promising for photonics applications due to the strong alteration of their optical properties compared to initial nonirradiated materials. We report our results on the synthesis and investigation of two kinds of these materials:

1. Photoinduced Au nanocomposites based on PMMA matrices, including bulk materials prepared by means of the polymerization technique;
2. photoinduced Ag nanocomposites with an organic–inorganic hybrid matrix based on TiO₂ gels.

The experimental data on evolution of absorption spectra of these materials due to laser irradiation at different wavelengths are presented. The linear and nonlinear refractive index changes in these materials owing to light-induced nanonstructuring are investigated.     

Investigation of halloysite nanotubes with deposited silver nanoparticles by methods of optical spectroscopy

Halloysite nanotube composites covered by silver nanoparticles with the average diameters of 5 nm and 9 nm have been studied by methods of optical spectroscopy of reflectance/transmittance and Raman spectroscopy. It has been established that silver significantly increases the light absorption by nanocomposites in the range of 300 to 700 nm with a maximum near 400 nm, especially for the samples with the nanoparticle size of 9 nm, which is explained by plasmonic effects. The optical absorption increases also in the long-wavelength spectral range, which seems to be due to the localized electronic states in an alumosilicate halloysite matrix after deposition of nanoparticles. Raman spectra of nanocomposites reveal intense scattering peaks at the local phonons, whose intensities are maxima for the samples with the silver nanoparticle sizes of 9 nm, which can be caused by plasmonic enhancement of the light scattering efficiency. The results show the ability to use halloysite nanotube nanocomposites in photonics and biomedicine.     

Stability, size and optical properties of silver nanoparticles prepared by laser ablation in different carrier media

We studied the effects of the surrounding liquid environment on the size and optical properties of silver nanoparticles prepared by laser ablation by a pulsed Nd:YAG laser operated at 1064 nm. The silver targets used were kept in acetone, water and ethanol. TEM observations and optical extinction were employed for characterization of particle size, shape and optical properties, respectively. Nano silver in acetone showed a narrow size distribution with a mean size of 5 nm and the colloidal solution was stable. In deionised water a rather narrow size distribution with a mean size of 13 nm was observed and nanoparticles were precipitated slowly after about two weeks. In ethanol, a broadening in size distribution and optical extinction spectra was observed. Silver nanoparticles in ethanol with a mean size of 22 nm were completely precipitated after 48 h. In acetone, deionised water and ethanol, the wavelengths of maximum optical extinction are 399, 405 and 411 nm respectively, which is attributed to increasing the size of the nanoparticles. Growth, aggregation and precipitation mechanisms were related to the dipole moment of the surrounding molecules in order to clarify the difference in size, optical properties and stability of the nanoparticles. PACS 79.20.Ds; 81.07.-b; 61.46.+w     

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.     

Growth of polymer–metal nanocomposites by pulsed laser deposition

Complex polymer–metal nanocomposites have a wide range of applications, e.g. as flexible displays and packaging materials. Pulsed laser deposition was applied to form nanostructured materials consisting of metal clusters (Ag, Au, Pd and Cu) embedded in a polymer (polycarbonate, PC) matrix. The size and amount of the metal clusters are controlled by the number of laser pulses hitting the respective targets. For Cu and Pd, smaller clusters and higher cluster densities are obtained as in the cases of Ag and Au due to a stronger reactivity with the polymers and thus a lower diffusivity. Implantation effects, differences in metal diffusivity and reactivity on the polymer surfaces, and the coalescence properties are discussed with respect to the observed microstructures on PC and compared to the metal growth on poly (methyl methacrylate), PMMA.     

Excimer laser-assisted annealing of silicate glass with ion-synthesized silver nanoparticles

The effect of KrF excimer laser radiation on a composite layer consisting of sodium-potassium silicate glass with silver nanoparticles is studied as a function of the number of laser nanosecond pulses. The silver nanoparticles are synthesized by ion implantation. The measured optical absorption of the composite layer demonstrates that the silver nanoparticle size decreases monotonically as the number of laser pulses increases. Rutherford backscattering shows that laser annealing is accompanied by silver diffusion into the bulk of the glass and partial metal evaporation from the sample surface. The detected decrease in the silver nanoparticle size is discussed in terms of simultaneous melting of silver nanoparticles and the glass matrix due to the absorption of laser radiation.     

Preparation of starch stabilized silver nanoparticles with spatial self-phase modulation properties by laser ablation technique

Silver nanoparticles inside the starch solution have been successfully fabricated by laser ablation of a silver plate immersed in starch solution. The ablation has been done using a Q-switched Nd:YAG laser at 10 Hz repetition rate. The starch solution allows for the formation of silver nanoparticles with uniform particle diameters and well dispersed. The ablation was performed at different time durations to study the influence of the laser ablation time on efficiency of particle formation and sizes. The Spatial Self-phase modulation phenomena which can determine the nonlinear optical property of the samples were also investigated for starch solutions containing silver nanoparticles.     

Electrical properties, structure, and surface morphology of poly(p-xylylene)–silver nanocomposites synthesized by low-temperature vapor deposition polymerization

The crystalline structure, surface morphology, electrical, and optical properties of thin films of nanocomposites consisting of silver nanoparticles embedded in poly(p-xylylene) matrix prepared by low-temperature vapor deposition polymerization were studied. Depending on the filler content, the average size of silver nanoparticles varied from 2 to 5 nm for nanocomposites with 2 and 12 vol.% of silver, correspondingly. The optical adsorption in the visible region due to surface plasmon resonance also exhibited a clear correlation from silver content, revealing a red shift of the adsorption peak with the increase of the metal concentration. The temperature dependences of the dc resistance of pure p-xylylene condensate and p-xylylene–silver cocondensates during polymerization as well as temperature dependences of the formed poly(p-xylylene)–silver nanocomposites were examined. The observed variation of the temperature dependences of electrical resistance as a function of silver concentration are attributed to different conduction mechanisms and correlated with the structure of the composites. The wide-angle X-ray scattering and AFM measurements consistently show a strong effect of silver content on the nanocomposite structure. The evolution of the size of silver nanoparticles by thermal annealing was demonstrated.     

Pulsed laser deposition of polymer-metal nanocomposites

Different polymer-metal nanocomposites, metal clusters on a polymer surface and for the first time also polymer/metal multilayers, were pulsed laser deposited at a wavelength of 248 nm. Poly(methyl methacrylate) (PMMA) and Bisphenol A dimeth-acrylate (BisDMA), which strongly differ in their hardness of 3 and 180 N/mm², respectively, were taken as polymer components. Metals Ag and Cu were chosen because of their different reactivity to polymers. When depositing Ag on PMMA, spherical clusters are formed due to high diffusion and total coalescence. For Cu, much smaller grains with partially elongated shapes occur because of lower diffusivity and incomplete coalescence. Compared to the results on the soft PMMA, the clusters formed on the harder BisDMA are much larger due to higher diffusivity on this underlayer. In PMMA/Cu multilayers, wavy layered structures and buckling is observed due to relaxation of compressive stress in the Cu layers. Smooth Cu layers with higher thicknesses can only be obtained, when the hardness of the polymer is sufficiently high, as in the case of BisDMA/Cu multilayers.     

Synthesis,characterization, conductivity and sensor application study of polypyrrole/silver doped nickel oxide nanocomposites

Conducting polymer composites of polypyrrole (PPy) and silver doped nickel oxide (Ag-NiO) nanocomposites were synthesised by in situ polymerisation of pyrrole with different contents of Ag-NiO nanoparticles. The formation of nanocomposites were studied by Fourier transform infrared (FTIR) and UV–vis spectroscopy, field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and AC and DC conductivity measurements. The sensitivity of ammonia gas through the nanocomposite was analysed with respect to different contents of nanoparticles. Spectroscopic studies showed the shift in the absorption bands of polymer nanocomposite than that of pure PPy indicating the strong interaction between the nanoparticles and polymer chain. FESEM revealed the uniform dispersion of nanoparticles with spherically shaped metal oxide particles in PPy matrix. The XRD pattern indicated a decrease in amorphous domain of PPy with increase in loading of nanoparticles. The higher thermal stability and glass transition temperature of polymer nanocomposites than that of pure PPy were revealed from the TGA and DSC respectively. The dielectric properties, DC and AC conductivity of nanocomposites were much higher than PPy and these electrical properties increases with the loading of nanoparticles. The nanocomposites showed an enhancement in sensitivity towards ammonia gas detection than PPy.     

Removal of doped poly(methylmetacrylate) from tungsten and titanium substrates by femto- and nanosecond laser cleaning

The influence of different laser pulse lengths on the removal of a polymer layer from metal substrates was investigated. As model systems, doped poly(methylmetacrylate) (PMMA) on titanium and tungsten substrates were selected.The ablation threshold and irradiation spot morphology of titanium and tungsten were compared for femtosecond (fs) and nanosecond (ns) laser irradiation and different pulse numbers. Nanosecond laser treatment resulted in a non-homogeneous surface morphology for both titanium and tungsten substrates. Femtosecond irradiation of tungsten revealed a homogeneous ablation spot with little changes in the surface morphology. For titanium, the formation of columnar structures within the irradiation spot was observed.Two different dopant concentrations were used for PMMA to achieve an equal linear absorption coefficient for the femto- and nanosecond laser wavelengths of 790 and 1064 nm. The best results were achieved for the removal of doped PMMA by femtosecond laser irradiation, where only a minimal modification of the metal surface was detected. In the case of nanosecond laser exposure, a pronounced change of the structure was observed, suggesting that damage-free cleaning of the selected metal may only be possible using femtosecond laser pulses. Different experimental parameters, such as laser fluence, pulse repetition rate and sample speed were also investigated to optimize the cleaning quality of doped PMMA from tungsten substrates with femtosecond laser pulses.     

Donor doping of single-walled carbon nanotubes by filling of channels with silver

The channels of single-walled carbon nanotubes (SWNTs) are filled with metallic silver. The synthesized nanocomposites are studied by Raman spectroscopy and optical absorption spectroscopy, and these data indicate a substantial modification of the electronic structure of the nanotubes upon their filling. Moreover, X-ray photoelectron spectroscopy shows that the incorporation of the metal leads to a change in the work function of SWNTs due to the Fermi level upshift and to the transfer of an electron density from inserted nanoparticles to the nanotube walls. Thus, the filling of the channels with silver results in donor doping of the nanotubes.     

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.     

激光烧蚀法制备的纳米金属胶体及表面的特性研究

本文利用Nd∶YAG激光器1064nm激发光照射金、银等贵金属,通过改变激发光的照射时间,制备出各种金、银胶体。对上述胶体进行了透射电镜(TEM)测量金属粒子的尺寸大小及形态表明这些胶体为粒径介于5～25nm的纳米体系,并对该体系进行了紫外—可见—近红外吸收光谱的研究;在制备胶体的同时还获得了纳米级粗糙金属表面,对该表面进行了扫描电镜(SEM)的测量。