Nanoporous carbon spheres and their application in dispersing silver nanoparticles

Monodisperse nanoporous carbon spheres (NCS) were synthesized in large quantities via a facile hydrothermal synthesis. It is found that the NCS have rough surfaces with a large quantity of uniformly distributed protruding and concaving zones. Large quantities of nanopores of about 0.3 nm in diameter are distributed uniformly on the whole sphere surfaces. The effects of reaction parameters on the surface roughness, sphere diameter and pore size of NCS were investigated. Taking the NCS as substrates, silver nanoparticles (NPs) were deposited onto their surfaces using a one-step ultrasonic electrodeposition procedure. The deposited silver NP has a uniform distribution, a high particle density and a narrow size range of 12-16 nm in diameter. This study demonstrates an efficient approach to fabricate noble-metal/carbon nanocomposites.     

Nonlinear optics of nontoxic nanomaterials

We studied the linear and nonlinear optical properties of halloysite nanotubes using Z-scan technique. Halloysite is alumina silicate clay rolled into 50 nm diameter hollow cylinders, where the silica layer is at the outer surface of the tube and alumina layer is in the inner surface. Optical absorption spectra show an absorption peak around 600 nm. Open aperture Z-scan measurements using 3 ns laser pulses at 532 nm reveal two-photon induced absorption. The closed aperture Z-scan indicates a positive nonlinear refractive index. As these nanotubes are nontoxic and biocompatible, they have advantages over conventional carbon nanotubes for biomedical applications.     

Gas flow sputtering: Versatile process for the growth of nanopillars, nanoparticles, and epitaxial thin films

Gas flow sputtering is a sputter-deposition method that enables soft and high-rate deposition even for oxides or nitrides. It involves sputtering at a high pressure of around 100 Pa and hollow cathode discharge in a tubular or parallel plate target with forced Ar flow. Depending on the sputtering conditions, various structures of magnetic materials are obtained, and some examples are shown in this paper. Co-Pt and Fe nanopillars are fabricated using a tubular target with a large inner diameter (6-40 mm). Fe nanoparticles with diameters ranging from a few nanometers to 150 nm are fabricated using a tubular target with a small inner diameter (5 mm). Magnetite epitaxial thin films are fabricated on MgO and GaAs substrates by substrate heating.     

Synthesis of hollow silver spheres using poly-(styrene-methyl acrylic acid) as templates in the presence of sodium polyacrylate

Hollow silver spheres were successfully prepared by reducing AgNO₃ with ascorbic acid and using negatively charged poly-(styrene-methyl acrylic acid) (PSA) spheres as templates in the presence of sodium polyacrylate as a stabilizer. Firstly, silver cations adsorbed on the surface of PSA spheres via electrostatic attraction between the carboxyl groups and silver cations were reduced in situ by ascorbic acid. The silver nanoparticles deposited on the surface of PSA spheres served as seeds for the further growth of silver shells. After that, extra amount of AgNO₃ and ascorbic acid solutions were added to form PSA/Ag composites with thick silver shells. In order to obtain compact silver shells, the as-prepared PSA/Ag composites were heated at 150 °C for 3 h. Then hollow silver spheres were prepared by dissolving PSA templates with tetrahydrofuran.     

TEM monitoring of silver nanoparticles formation on the surface of lead crystal glass

Silver nanoparticles have been formed on the surface of lead crystal glass by means of (i) ion-exchange of alkaline ions from the glass by Ag⁺ ions from a molten salts bath, and (ii) silica based sol-gel coatings containing silver. All experimental variables concerning both ion-exchange process and sol-gel coatings application were combined and studied as main parameters governing the reduction of Ag⁺ ions to Ag⁰ atoms and further aggregation to form nanosized colloids. The content of thermoreducing agents (arsenic or antimony oxides) in the lead crystal glass was essential to favour the reduction of silver ions to form nanoparticles. Optimal experimental conditions to be used for the obtaining of surface silver nanoparticles were determined. TEM was used as the principal characterisation technique for direct observation of the nanoparticles generated. The size of silver colloids varied in the 20-300 nm range for ion-exchanged samples and in the 10-80 nm range for sol-gel coated samples.     

Synthesis of PMA stabilized silver nanoparticles by chemical reduction process under a two-step UV irradiation

Poly(methacrylic acid) (PMA) stabilized silver nanoparticles (Ag NPs), also used in the surface modification of clothing fibers, were fabricated via chemical reduction processes under UV irradiation. To obtain an uniform size distribution it has been designed a new “two-step” process which employs two different UV radiation densities in order to control the kinetics of NPs nucleation. The as produced nanoparticles were characterized by UV-vis absorption spectroscopy and TEM microscopy. The results show the reduction of the Ag ions and the nanoparticles nucleation in the first step. In the second step, the final Ag NPs size distribution is controlled through a quick cross-linking of the PMA that freezes out any further modification. A narrow size distribution with more than 80% NPs smaller than 10 nm and none larger than 25 nm was obtained and the long-term stability (one month) of the colloidal solution was verified.     

中空Ag纳米球壳的制备及性能表征

 以改性聚苯乙烯微球为模板,采用化学镀法在聚苯乙烯微球表面包覆一层银,在四氢呋喃溶液中将聚苯乙烯微球溶解,得到中空Ag纳米球壳。采用扫描电镜、透射电镜和X射线衍射仪对样品进行了表征及分析,并用紫外可见分光光度计研究了粒子的光学性质。实验结果表明：运用此法成功地制备出中空Ag纳米球壳的内径为250 nm,壁厚约为15 nm,并且成功地使纳米粒子的紫外吸收光谱由600 nm红移至900 nm左右,实现了在可见光至近红外光区调节Ag纳米结构的吸收峰。     

High-efficiency optical compression of Ti:sapphire laser pulses at 800 nm using a silver-coated hollow fiber

A 50 cm silver coated hollow fiber with inner diameter of 250 μm and filled with argon has been used to compress optical pulses from a Ti:sapphire laser at 800 nm. Input pulses with energy of 250 μJ and duration of 110 fs were used and compressed pulses with energy of 220 μJ and duration of 20 fs were generated by using a prism compressor. Numerical and experimental results are compared. There is good agreement between the measured beam diameters of the hollow-fiber output pulse and the calculated values obtained from propagation of the HE₁₁ mode into free space. For comparison, a similar uncoated fused-silica hollow fiber was also used to obtain 20 fs compressed pulses with an energy of 190 μJ. Received: 7 September 2002 / Published online: 26 March 2003 RID="*" ID="*"Corresponding author. Fax: +1-780/492-1811, E-mail: mohebbi@ee.ualberta.ca     

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.     

In-situ formation of silver nanoparticles stabilized by amphiphilic star-shaped copolymer and their catalytic application

Silver nanoparticles (Ag NPs) were prepared via in situ reduction of silver nitrate (AgNO₃) using polymeric micelles as nanoreactors without any additional reductant. The micelles were constructed from the amphiphilic star-shaped copolymer composed of poly(?-caprolactone) (PCL) segment, 2-(dimethylamino)ethyl methacrylate (DMAEMA or DMA) units and oligo(ethylene glycol)monomethyl ether methacrylate (OEGMA or OEG) units. The Ag NPs stabilized by those star-shaped copolymers were characterized using UV-vis spectrum, DLS, TEM and FTIR. It confirmed that PDMAEMA exhibited the reducing property unless pH was above 7. The Ag NPs were sphere-like with a diameter of 10-20 nm, which was independent of the architecture of the copolymer and AgNO₃ concentration. Furthermore, the catalytic activity of these Ag NPs was investigated by monitoring the reduction of p-nitrophenol (4-NP) by NaBH₄. The result showed that the Ag NPs formed by coordination reduction can be effectively applied in catalytic reaction.     

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.     

Synthesis and characterization of hard magnetic composites—Hollow microsphere/titania/barium ferrite

Hard magnetic composites—hollow microsphere (core)/titania (intermediate layer)/barium ferrite (magnetic shell) (M/T/B) were prepared by wet-chemical method. Barium ferrite nanoparticles were directly coated on the rutile titania-coated hollow microsphere forming light hard magnetic composites using sol-gel technique. The prepared composites were characterized with FESEM, EDS, XRD and vibrating sample magnetometry. The composites are composed of barium ferrite, hematite, titania and mullite. For the samples with 40 wt.% barium ferrite, its specific saturation magnetization with titania is increased to 17.88 emu/g in comparison with 9.6 emu/g without titania. The function of titania in the composites is also discussed.     

Rapid synthesize of gold nanoparticles by microwave irradiation method and its application as an optical limiting material

We present rapid synthesis of gold nanoparticles by microwave irradiation method. Sample with average particle size 7.7 nm is obtained from TEM. Linear and nonlinear optical studies of the prepared samples are discussed. Reverse saturable absorption (RSA) at longitudinal surface plasmon resonance (SPR) in gold nanoparticles (Au NPs) have been observed using Z-scan and transient absorption techniques with 532 nm laser pulses. Such RSA behavior makes Au NPs an ideal candidate for optical limiting applications.     

Integral fluorescence enhancement by silver nanoparticles controlled via PMMA matrix

The metal-enhanced fluorescence is measured with different thickness of emission film. Silver nanoparticles are immobilized on glass slide by chemical self-assembly method. Rhodamine B molecules are dispersed in the polymer matrix of Poly(methyl methacrylate) (PMMA), then spin coated on prepared silver particles substrate with different thickness from 15 nm to 70 nm. The enhanced fluorescence is observed depending on the thickness of emission film since the average distance between rhodamine B molecules and silver nanoparticles is altered by the PMMA matrix. The 5-fold enhancement is attained. The experiment was explained qualitatively by an integral fluorescence enhancement.     

Structural features of natural and acids modified chrysotile nanotubes

The structural features of the natural chrysotile have been studied by transmission electron microscopy, scanning electron microscopy, energy-dispersive X-ray spectrometry, thermogravimetric and low-temperature nitrogen adsorption techniques. The chrysotile fibers are present as nanotubes of cylindrical morphology of various forms (rectilinear cylinders, cylinders with cup-like ends, tube twins, cylinder-in-cylinder and cone-in-cone tubes) with the outer diameters of 15-30 nm and the inner ones of 2-6 nm. The surface areas of the raw and the acid leached chrysotile samples obtained by nitrogen adsorption are 15.3 and 63.6 m²/g with the average pore diameter 9.8 and 3.9 nm, respectively. The inner and the outer surfaces of the chrysotile nanotubes are evaluated by the geometric method as 16 and 80 m²/g. The thermogravimetric analysis reveals two main phases of mass loss associated with dehydration and dehydroxylation (with two overlaying steps) processes. The first phase is attributed to the dehydration reaction at low temperature range 293-450 K with activation energy in the range 22-32 kJ/mol. The second phase occurs between 798 and 985 K with activation energy 249-298 kJ/mol for the raw sample and 130-146 kJ/mole for the acid treated one.     

Silver aggregates and twofold-coordinated tin centers in phosphate glass: A photoluminescence study

The optical properties of silver species in various oxidation and aggregation states and of tin centers in melt-quenched phosphate glasses have been assessed by optical absorption and photoluminescence (PL) spectroscopy. Glasses containing silver and tin, or either dopant, were studied. Emission and excitation spectra along with time-resolved and temperature-dependent PL measurements were employed in elucidating the different emitting centers observed and investigating on their interactions. In regard to silver, the data suggests the presence of luminescent single Ag⁺ ions, Ag⁺-Ag⁺ and Ag⁺-Ag⁰ pairs, and nonluminescent Ag nanoparticles (NPs), where Ag⁺-Ag⁰→Ag⁺-Ag⁺ energy transfer is indicated. Tin optical centers appear as twofold-coordinated Sn centers displaying PL around 400 nm ascribed to triplet-to-singlet electronic transitions. The optically active silver centers were observed in glasses where 8 mol% of both Ag₂O and SnO, and 4 mol% of Ag₂O were added. Heat treatment (HT) of the glass with the high concentration of silver and tin leads to chemical reduction of ionic silver species resulting in a large volume fraction of silver NPs and the vanishing of silver PL features. Further characterization of such heat-treated glass by transmission electron microscopy and X-ray photoelectron spectroscopy appears consistent with silver being present mainly in nonoxidized form after HT. On the other hand, HT of the glass containing only silver results in the quenching of Ag⁺-Ag⁰ pairs emission that is ascribed to nonradiative energy transfer to Ag NPs due to the positioning of the pairs near the surface of NPs during HT. In this context, an important finding is that a faster relaxation was observed for this nanocomposite in relation to a heat-treated glass containing both silver and tin (no silver pairs) as revealed by degenerate four-wave mixing spectroscopy. Such result is attributed to Ag NP→Ag⁺-Ag⁰ plasmon resonance energy transfer. The data thus indicates that energy transfer between Ag⁺-Ag⁰ pairs and NPs is bi-directional.     

Fabrication of silver stabilization layer of coated conductor using organic silver complexes

Silver stabilizing layer of coated conductor has been prepared by dip coating method using organic silver complexes containing 10 wt.% silver as a starting material. Coated silver complex layer was dried in situ with hot air and converted to crystalline silver by post heat treatment in flowing oxygen atmosphere. A dense continuous silver layer with good surface coverage and proper thickness of 230 nm is obtained by multiple dip coatings and heat treatments. The film heat treated at 500 °C showed good mechanical adhesion and crystallographic property. The interface resistivity between superconducting YBCO layer and silver layer prepared by dip coating was measured as 0.67 × 10⁻¹³ Ω m².     

Preparation and magnetic properties of anisotropic (Sm,Pr)Co5/Co composite particles

Anisotropic (Sm,Pr)Co₅/Co nanocomposite particles have been fabricated by chemical coating the 2 h ball milled (Sm,Pr)Co₅ flakes with Co nanoparticles. The Co nanoparticles were synthesized with mean particle sizes in the range of 20-50 nm. The nanocomposite particles present [0 0 1] out-of-plane texture and improved magnetic properties, e.g., an enhanced remanent magnetization of 72 emu/g for (Sm,Pr)Co₅/Co and 66 emu/g for (Sm,Pr)Co₅. In addition, by using the 8 h ball milled powders (much smaller than the 2 h ball milled powders) as the starting materials, Co nanoparticles can also be successfully coated on the surface of the flakes. A plausible mechanism for the formation of Co nanoparticles on the surface of (Sm,Pr)Co₅ flakes is discussed.     

Facile fabrication of novel cyclomatrix-type polyphosphazene nanotubes with active hydroxyl groups via an in situ template approach

Novel polyphosphazene nanotubes with active hydroxyl groups were fabricated via an in situ template approach under ultrasonic irradiation. SEM and TEM results indicated that the nanotubes were uniform with length of several micrometers, inner diameter of ca. 20 nm and outer diameter of 60-80 nm. FTIR spectra revealed that the content of the hydroxyl groups on the nanotube surface was dependent on the feed ratio of hexachlorocyclotriphosphazene (HCCP) to 4,4′-sulfonyldiphenol. The successful esterification of polymer nanotubes with benzoxy chloride demonstrated the high reactivity of the hydroxyl groups. The method employed here might provide a simple and effective way to prepare functional nanotubes used for biological applications.     

Designable formation of metal nanoparticle array with the deposition of negatively charged nanoparticles

Ultrafine gold and platinum nanoparticles (NPs) were fabricated by pulsed laser ablation in helium gas and the NPs 2-15 nm in diameter were selectively classified by an electrostatic size-selection technique employing a low-pressure differential mobility analyzer (LP-DMA). The spherical NPs obtained showed a narrower distribution of diameters of anionic NPs over cationic NPs. With this knowledge, the anionic NPs were deposited onto silicon substrates designed by electron beam lithography processing, and designable patterns of arrayed NPs were produced by removing the photoresist layer.