Surface modification of magnetic metal nanoparticles through irradiation graft polymerization

To tailor the interfacial interaction in magnetic metal nanoparticles filled polymer composites, the surfaces of iron, cobalt and nickel nanoparticles were grafted by irradiation polymerization. In the current report, effects of grafting conditions, including irradiation atmosphere, irradiation dose and monomer concentration, on the grafting reaction are presented. The interaction between the nanoparticles and the grafted polymer was studied by thermal analysis and X-ray photoelectron spectrometry. It was found that there is a strong interfacial interaction in the form of electrostatic bonding in the polymer-grafted nanoparticles. The dispersibility of the modified nanoparticles in chloroform was significantly improved due to the increased hydrophobicity.     

Surface modification of gold nanoparticles and their monolayer behavior at the air/water interface

Gold nanoparticles were prepared by two different methods. The first method was chemically grafting the particles with different lengths of alkylthiol (C₆SH, C₁₂SH and C₁₈SH). For the second method, the Au particles were surface modified first by mercaptosuccinic acid (MSA) to render a surface with carboxylic acid groups which play a role to physically adsorb cationic surfactant in chloroform. This method was termed physical/chemical method. In the first method, the effects of alkyl chain length and dispersion solvent on the monolayer behavior of surface modified gold nanoparticles was evaluated. The gold nanoparticles prepared by 1-hexanthiol demonstrated the narrowest size distribution. Most of them showed narrower particle size distributions in chloroform than in hexane. For the physical/chemical method, the particles can spread more uniformly on the water surface which is attributed to the amphiphilic character of the particles at the air/water interface. However, the particles cannot pack closely due to the relatively weak particle-particle interaction. The effect of alkyl chain length was also assessed for the second method.     

Surface modification of magnetic nanoparticles in biomedicine

Progress in surface modification of magnetic nanoparticles(MNPs)is summarized with regard to organic molecules,macromolecules and inorganic materials.Many researchers are now devoted to synthesizing new types of multi-functional MNPs,which show great application potential in both diagnosis and treatment of disease.By employing an ever-greater variety of surface modification techniques,MNPs can satisfy more and more of the demands of medical practice in areas like magnetic resonance imaging(MRI),fluorescent marking,cell targeting,and drug delivery.     

Surface energy modification by electron beam

We observe a pronounced variation of wettability properties in solid state materials induced by a low-energy electron beam. The phenomenon occurs in several stages characterized by various mechanisms. We show that for low electron doses the irradiation leads to decrease in the wetting of a dielectric surface due to induced surface electric potential. The higher electron charge leads to formation of a chemical monolayer on material’s surface. It has been found that the electron irradiation strongly modifies the surface free energy of SiO₂ by decreasing its total surface free energy value, almost twice. However, electron-induced variations of dispersive and polar components of the surface free energy are quite different and depend of incident electron charge.     

Laser assisted embedding of nanoparticles into metallic materials

This paper reports a methodology of half-embedding nanoparticles into metallic materials. Transparent and opaque nanoparticles are chosen to demonstrate the process of laser assisted nanoparticle embedding. Dip coating method is used to coat transparent or opaque nanoparticle on the surface of metallic material. Nanoparticles are embedded into substrate by laser irradiation. In this study, the mechanism and process of nanoparticle embedding are investigated. It is found both transparent and opaque nanoparticles embedding are with high densities and good uniformities.     

Surface modification of ceria nanoparticles and their chemical mechanical polishing behavior on glass substrate

To improve their chemical mechanical polishing (CMP) performance, ceria nanoparticles were surface modified with γ-aminopropyltriethoxysilane (APS) through silanization reaction with their surface hydroxyl group. The compositions, structures and dispersibility of the modified ceria particles were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), field-emission scanning electron microscopy (FE-SEM), energy dispersive spectroscopy (EDS), laser particle size analyzer, zeta potential measurement and stability test, respectively. The results indicated that APS had been successfully grafted onto the surface of ceria nanoparticles, which led to the modified ceria nanoparticles with better dispersibility and stability than unmodified ceria particles in aqueous fluids. Then, CMP performance of the modified ceria nanoparticles on glass substrate was investigated. Experimental results showed that the modified ceria particles exhibited lower material removal rate (MRR) but much better surface quality than unmodified ceria particles, which may be explained by the hardness reduction of ceria particles, the enhancement of lubrication of the particles and substrate surfaces, and the elimination of the agglomeration among the ceria particles.     

Preparation and optical properties of ZnO@PPEGMA nanoparticles

The poly(poly(ethylene glycol) methyl ether monomethacrylate) (PPEGMA) grafted zinc oxide (ZnO) nanoparticles were successfully prepared via the surface-initiated atom transfer radical polymerizations (ATRP) from the surfaces functionalized ZnO nanoparticles. The 2-bromoisobutyrate (BIB) was immobilized onto the surface of the ZnO nanoparticles through the reaction between 2-bromoisobutyryl bromide (BIBB) and the hydroxyl groups on nanoparticles, serving as the initiator to induce the ATRP of poly(ethylene glycol) monomethacrylate (PEGMA). Well-defined polymer chains were grown from the surfaces to yield hybrid nanoparticles comprised of ZnO cores and PPEGMA polymer shells having multifunctional end groups. The structure and morphology of the nanoparticles were characterized using Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), X-ray diffraction (XRD) and transmission electron microscopy (TEM). The optical properties of the nanoparticles were investigated by UV-vis absorption spectroscopy and photoluminescence spectroscopy (PL). The results showed that the dispersion and near-band edge (NBE) emission of ZnO nanoparticles could be improved by the grafted PPEGMA polymer segments.     

Surface modification of polyvalent element-containing glasses

Seven soda-lime silicate glasses, each of which contains one of the following polyvalent metals: Fe, Mn, Cu, Ce, Ti, V, and Cr, are oxidized in air and reduced in H₂/N₂ (1/99) at their respective glass transition temperature for some period. A crystalline oxide surface layer is created on the glasses (except the vanadium-bearing glass) under the oxidizing condition, since the metallic ions are oxidized from lower to higher valence state, and thereby calcium ions diffuse outward and react with oxygen ions. In contrast, a silica-rich surface layer is created on the glasses under the reducing condition, since sodium and calcium ions diffuse inward. It is found that the extents of both outward and inward diffusions strongly depend on the type of the polyvalent ions for the same conditions of heat-treatment. Out of the seven polyvalent metals studied in this work, copper induces the highest extent of both the inward and outward diffusion, and hence, the thickest surface layer of both amorphous silica and crystalline alkaline earth oxides. The oxide layer lowers the onset temperature of the primary crystallization. The silica-rich surface layer enhances the chemical resistance of the glass in a hot basic solution.     

Surface modification for the perfluorosulfonate proton-conducting electrolyte membrane

The positively charged ions of palladium particles are obtained by reducing the solution containing metallic ions in the presence of PDDA (poly-diallyldimethylammonium chloride) medium. The nascent palladium particles are dispersed evenly on the surface of the perfluorosulfonate proton-conducting electrolyte membrane and bonded firmly to the activation center of the membrane. The mechanical strength of membrane is greatly enhanced by surface modification. And the methanol diffusion coefficients of the modified membrane are decreased prominently by the deposition of palladium particles on the surface, which serves as a natural barrier for methanol crossing.     

表面修饰基团对金纳米颗粒非线性光学效应的影响研究

采用两相法分别制备一级硫醇修饰和二级十六烷基三甲基溴化铵(CTAB) 修饰的金纳米颗粒,通过透射电子显微镜和紫外-可见吸收光谱表征了其结构和线性光学性质. 采用开孔Z扫描技术,研究表面修饰对金纳米颗粒在532 nm波长激光作用下的非线性光学效应及光限幅性能的影响行为.结果表明,二级CTAB的修饰增强了颗粒在激光照射下的局域场作用, 并提高了热电子对非线性光学效应的贡献程度,从而有效地提高了金纳米颗粒的光限幅性能.     

Cavity ring-down spectroscopy of metallic gold nanoparticles

The optical properties of supported gold nanoparticles with sizes of 1.3 nm, 1.6 nm, 2.5 nm, and 2.9 nm have been studies by using cavity ring-down spectroscopy in the photon energy range between 1.8 eV and 3.0 eV. The obtained results show the possibility to obtain optical information of nanoassembled materials with high sensitivity. The experimental findings are compared to calculations using Mie-Drude theory. Whereas the broadening of the surface plasmon resonance with decreasing size is well described by this model, the observed blue-shift of the surface plasmon resonance contradicts the predictions of the Mie-Drude theory. The latter effect can be explained by the presence of a skin region with decreased polarizability typical for coinage metal particles. Furthermore, it is found that the supported gold nanoparticles are robust under ambient conditions, an important issue when using these materials for optical applications.     

Size controlled synthesis of Co nanoparticles by combination of organic solvent and surfactant

Co particles were synthesized with mean particle sizes in the range of 3.2-171.4 nm in ambient atmosphere by reduction of cobalt salt with sodium borohydride as the reducing reagent, a combination of alcohols as solvents and a triblock copolymer P123 (EO₂₀PO₇₀EO₂₀) as the surfactant. The particle size and its distribution were controlled by varying the synthesis parameters such as the viscosity of the medium, the amount of alcohols or P123 in the reaction system. FT-IR and X-ray photoelectron spectroscopy (XPS) measurements confirmed the interaction between the oxygen atoms of P123 and Co²⁺ or Co⁰. Detailed surface analyses by XPS and HRTEM revealed that the synthesized particles consisted of Co⁰ metal surrounded by amorphous CoO, Co₂B and chemisorbed P123.     

Aqueous immune magnetite nanoparticles for immunoassay

Immune magnetite nanoparticles (MNPs) are prepared by four successive reactions, which are MNPs preparation, silica-coating, surface modification with amino group, and conjugation with bio-molecule, respectively. The crystal structure and morphology of intermediate products are characterized by XRD, TEM and AFM. Qualitative and quantitative assays for amino group on the MNPs’ surface are made by FTIR and Organic Element Assay. Ultraviolet–visible absorption spectrum can indirectly illustrate the quantity of bio-molecule conjugated with MNPs. In addition, specific combination and nonspecific combination of immune MNPs are measured by commercial RIA box. The results show that the size of MNPs prepared is 10 ± 5 nm, and silica-coated MNPs with spinel structure have quasi-spherical morphology. Infrared absorption bands of –NH₂ are appeared around 3380–3200 cm⁻¹ and 1650–1510 cm⁻¹, and the amino group content is 0.5 μmol –NH₂ per mg MNPs. The specific immune combination of immune MNPs is up to 75%, and nonspecific combination is under 5%.     

Synthesis of mixed metallic nanoparticles by spark discharge

Short spark discharges (2 μs) were successfully applied to generate mixed particles a few nanometres in diameter by fast quenching. Alloyed Cr–Co electrodes were applied to demonstrate this. Further it was shown that if the anode and the cathode are different materials, the discharge process mixes the vapour of both materials, forming mixed nanoparticles. Electron microscopy (TEM, SEM), energy dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD) analyses were performed on the collected particles to study their size, morphology, composition and structure. The average compositions of the particles were measured by inductively coupled plasma (ICP). In addition, online measurements of the particle size distribution by mobility analysis were carried out. In the case of alloyed electrodes (Cr–Co), the relative concentration of the elements in the nanoparticulate sample was consistent with the electrode composition. When using electrodes of different metals (Au–Pd and Ag–Pd) the individual nanoparticles showed a range of mixing ratios. No surface segregation was observed in these mixed noble metal particles. Crystalline nanoparticulate mixed phases were found in all cases.     

Surface modification of polyacrylonitrile-based carbon fiber and its interaction with imide

In this work, sized polyacrylonitrile (PAN)-based carbon fibers were chemically modified with nitric acid and maleic anhydride (MA) in order to improve the interaction between carbon fiber surface and polyimide matrix. Bismaleimide (BMI) was selected as a model compound of polyimide to react with modified carbon fiber. The surface characteristic changing after modification and surface reaction was investigated by element analysis (EA), scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and surface enhanced Raman scattering (SERS). The results indicated that the modification of carbon fiber surface with MA might follow the Diels Alder reaction mechanism. In the surface reaction between modified fibers and BMI, among the various surface functional groups, the hydroxyl group provided from phenolic hydroxyl group and bridged structure on carbon fiber may be the most effective group reacted with imide structure. The results may shed some light on the design of the appropriate surface structure, which could react with polyimide, and the manufacture of the carbon fiber-reinforced polyimide matrix composites.     

Generation of nanoparticles by spark discharge

The production of nanoparticles by microsecond spark discharge evaporation in inert gas is studied systematically applying transmission electron microscopy, mobility analysis and BET surface area measurement. The method of spark discharge is of special interest, because it is continuous, clean, extremely flexible with respect to material, and scale-up is possible. The particle size distributions are narrow and the mean primary particle size can be controlled via the energy per spark. Separated, unagglomerated particles, 3–12 nm in size, or agglomerates can be obtained depending on the flow rate. The nanoparticulate mass produced is typically 5 g/kWh. A formula is given, which estimates the mass production rate via thermal conductivity, evaporation enthalpy and the boiling point of the material used. We showed that with gas purified at the spot, the method produced gold particles that were so clean that sintering of agglomerated particles occurred at room temperature. The influence of a number of parameters on the primary particle size and mass production rate was studied and qualitatively understood with a model of Lehtinen and Zachariah (J Aerosol Sci 33:357–368, 2002). Surprisingly high charging probabilities for one polarity were obtained. Spark generation is therefore of special interest for producing monodisperse aerosols or particles of uniform size via electrical mobility analysis. Qualitative observations in the present study include the phenomenon of material exchange between the electrodes by the spark, which opens the possibility of producing arbitrary mixtures of materials on a nanoscale. If spark generation of nanoparticles is performed in a standing or almost standing gas, an aerogel of a web-like structure forms between surfaces of different electrical potential.     

Synthesis of low-melting-point metallic nanoparticles with an ultrasonic nanoemulsion method

A one-step, economical nanoemulsion method has been introduced to synthesize low-melting-point metallic nanoparticles. This nanoemulsion technique exploits the extremely high shear rates generated by the ultrasonic agitation and the relatively large viscosity of the continuous phase - polyalphaolefin (PAO), to rupture the molten metal down to diameter below 100 nm. Field’s metal nanoparticles and Indium nanoparticles of respective average diameters of 15 nm and 30 nm have been obtained. The nanoparticles size and shape are determined by transmission electron microscopy (TEM). Their phase transition behavior is examined using a differential scanning calorimeter (DSC). It is found that these nanoparticles dispersed in PAO can undergo reversible, melting-freezing phase transition, and exhibit a relatively large hysteresis. The experimental results suggest that the nanoemulsion method is a viable route for mass production of low-melting nanoparticles.     

Surface modification and characterization of magnesium hydroxide sulfate hydrate nanowhiskers

In order to enhance the compatibility with plastic polymers, magnesium hydroxide sulfate hydrate (MHSH) nanowhiskers were modified through grafting methyl methacrylate (MMA) on the surface of the nanowhiskers by emulsion polymerization. The influences of the reaction time, MMA monomer content, adding speed of monomer and the reaction temperature on the grafting ratio were investigated. Thermogravimetry (TG), Fourier transform infrared (FT-IR) spectroscopy, X-ray powder diffraction (XRD), scanning electron microscope (SEM), energy-dispersive X-ray (EDX) spectroscopy and surface contact angle measurement were used to characterize the effect of surface modification. The results showed that the MHSH nanowhiskers were uniformly coated by polymethyl methacrylate (PMMA), and a well-defined core-shell hybrid structure of MHSH/PMMA was obtained. The surface contact angle of the hybrid whiskers increased to 87.32° from 12.71° and the whiskers surface was changed from hydrophilic to lipophilic.     

Electroless deposition of silver on synthesized calcite via surface modification

Metallic silver was deposited on the surface of synthesized calcite via a simple electroless deposition method. Calcite with cubic morphology was prepared first by homogeneous precipitation and it was subsequently surface modified using ammonium oxalate. The electroless deposition was carried out using formaldehyde as the reducing agent and silver nitrate as the silver source. Both calcite and the silver deposited calcite were characterized by different techniques. Surface modification of calcite with ammonium oxalate is necessary for the deposition of silver and the size of the deposited silver particles could be controlled by changing the deposition parameters such as concentration of the reagents and the deposition time. Lower concentration of silver ions (e.g. 0.01 M AgNO₃) and shorter deposition times (e.g. 30 min) lead to the formation of silver nanoparticles on calcite.     

Surface plasmon resonance of Ag nanoparticles in the vicinity of a high impedance surface

Surface Plasmon resonance of Ag nanoparticles in the vicinity of a high impedance surface is investigated. Mushroom-like nanostructures were vertically grown on silicon substrate to form a high impedance surface operating in the range of optical frequencies. Formation of Ag nanoparticles on the fabricated high impedance surface was realized using plasma bombardment process. Optical measurements show an enhancement in the surface plasmon resonances of Ag nanoparticles. Also it was shown that the plasmon resonance peak of the Ag nanoparticles shifts to blue when Ag nanoparticles approach to the high impedance surface.