Photoinduced formation and aggregation of silver nanoparticles at the surface of carboxymethylcellulose films

Formation and aggregation of photolytic silver nanoparticles at the surface of silver salt of carboxymethylcellulose films (CMCAg films) have been investigated. Detailed X-ray photoelectron spectroscopy (XPS) study and field emission type scanning electron microscopy (FE-SEM) observation have been carried out to characterize silver nanoparticles at the film surface. When the CMCAg films were irradiated with UV light in wet air at room temperature for 30–60 min, silver nanoparticles of ca. 10 nm size were formed at the irradiated surface. According to the FE-SEM observation, the growth of the particle diameter and aggregation of nanoparticles took place after prolonged irradiation, and finally, the irradiated side of the film surface was densely covered with the silver nanoparticles of ca. 35 nm size. Chemical composition analysis by the XPS measurements has confirmed the increase in the atomic concentration of silver with irradiation time. It is suggested that silver atoms and clusters can move in the film and precipitate at the irradiated surface.     

Ag-PVP复合薄膜的制备及其光谱特性

在聚乙烯吡咯烷酮 ( PVP)乙醇溶液中以硝酸银为原料 ,采用旋涂法 ( spin coating)原位合成了 Ag- PVP复合薄膜。由于薄膜表面 Ag胞质团的共振吸收 ,所以在 430～ 45 0 nm范围内薄膜的吸收光谱有一较尖锐的吸收峰 ,随热处理温度的升高 ,吸收峰增强、变宽。采用复合介质理论计算了 Ag- PVP复合薄膜的吸收光谱 ,实验结果和理论计算相一致。     

ESCA studies of nitrogen-containing stainless steels

ESCA examination of films formed on nitrogen-containing stainless steels after immersion in 0.1 M NaCl revealed that nitrogen was enriched in the outer 0.5 nm of the film at a concentration a few times higher than in the substrate. The N(1s) binding energy varied from 399.6–399.7 eV at the outermost surface of the film to 398.3–398.8 eV in the film at a depth of about 0.5 nm. This indicates a change in the chemical state of nitrogen upon exposure of the nitrogen-containing stainless steels to the solution, and furthermore, that the surface nitrogen enrichment could be of significance in the improved pitting resistance.     

Spatially controlled dissolution of Ag nanoparticles in irradiated SiO2 sol-gel film

In this paper, we report the spatially controlled dissolution of silver nanoparticles in irradiated SiO₂ sol-gel films. The Ag nanoparticles have been formed in the sol-gel solution before the film deposition by adding Triton and ascorbic acid and also after the film deposition using a heat treatment at 700 °C for few minutes or at 550 °C for 6 h in reducing atmosphere. Using a spectrometer, a new view white light interferometer and a micro-thermal analyzer, we demonstrate that the silver nanoparticles can be dissolved using a continuous black ray UV lamp or with a near-infrared (NIR) femtosecond laser, due to a significantly increase in the local temperature. We confirm that the micro-thermal analyzer can be used as a new tool to study the dissolution of metallic nanoparticles in thin film if located at the surface of the films.     

Optical and structural properties of CdS thin films grown by chemical bath deposition doped with Ag by ion exchange

In this work thin CdS films using glycine as a complexing agent were fabricated by chemical bath deposition and then doped with silver (Ag), by an ion exchange process with different concentrations of AgNO₃ solutions. The CdS films were immersed in silver solutions using different concentrations during 1 min for doping and after that the films were annealed at 200 °C during 20 min for dopant diffusion after the immersion on the AgNO₃ solutions. The aim of this research was to know the effects of different concentrations of Ag on the optical and structural properties of CdS thin films. The optical band gap of the doped films was determined by transmittance measurements, with the results of transmittance varying between 35% and 70% up to 450 nm in the electromagnetic spectra and the band gap varying between 2.31 and 2.51 eV depending of the silver content. X-ray photoelectron spectroscopy was used to study the influence of silver on the CdS:Ag films, as a function of the AgNO₃ solution concentration. The crystal structure of the thin CdS:Ag films was studied by the X-ray diffraction method and the film surface morphology was studied by atomic force microscopy. Using the ion exchange process, the CdS films’ structural, optical and electric characteristics were modified according to silver nitrate concentration used.     

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.     

Effect of aluminum on the corrosion behavior of NiTiAl thin films

An electrochemical study for the evaluation of corrosion behavior using potentiodynamic and Tafel techniques was conducted in 0.9% NaCl solution on Ni-Ti and Ni-Ti-Al shape memory thin films. Atomic force microscopy (AFM) and electron probe microanalyzer (EPMA) were applied to observe morphology of the surface film and elemental distribution, respectively, prior to and after immersion in 0.9% NaCl solution. The concentration of dissolved Ni from Ni-Ti-Al thin films in the electrolyte, measured with inductively coupled plasma atomic emission spectrometer (ICP-AES), was significantly lower after immersion for 7 days, as compared to Ni-Ti thin film. This demonstrated that a better corrosion resistance and lower corrosion current density were revealed for Ni-Ti-Al thin films than that for Ni-Ti thin film. The improved corrosion performance of Ni-Ti-Al thin films would be potentially beneficial for related biological applications. This was attributed to the introduction of aluminum after exposure to an aqueous environment.     

纳米银粒子复合膜的制备及光学性质测量

本文介绍了一种制备纳米复合薄膜的简易方法.以银胶为纳米粒子的来源,将银粒子渗入明胶基质中,成功地制备出纳米银粒子明胶复合膜及染料(FS,Rh6G)包覆纳米银粒子的复合膜.并报道了所制备的复合膜的电镜(TEM)、吸收谱和荧光光谱测量结果.     

Synthesis and characterization of conductive silver ink for electrode printing on cellulose film

Silver nanoparticles with size less than 50 nm were synthesized from silver nitrate, polyvinylpyrrolidone (PVP) and ethylene glycol, where these chemicals acted as metal precursor, stabilizer and reducing agent, respectively. Then a conductive silver ink was prepared with a suitable solvent by adding a viscosifier, hydroxyethyl-cellulose (HEC), and a surfactant, diethylene glycol (DEG). The combined effect of both viscosifier and surfactant on the physical property of the silver ink was analyzed by measuring the contact angle of the silver ink on a cellulose film. Moreover, the influences of PVP molecular weight and reaction temperature on the size of the silver nanoparticles were analyzed. Then the silver ink was coated on the cellulose film by spin coating and the effects of different solvents, sintering temperatures and solid contents on its electrical resistivity were examined. It was found that, with 50 % co-solvent of deionized water and DEG and solid content of around 50 %, the silver ink exhibited the lowest resistivity. This ink can be used for inkjet printing of conductive patterns on cellulose films.     

Synthesis and characterization of silver-polypyrrole film composite

In this work, we report the chemical polymerization of pyrrole to obtain thin film of polypyrrole (PPy) hydrochloride deposited onto the electrode of the quartz crystal microbalance (QCM). The film in the base form was exposed to a solution of AgNO₃. Electroless reduction for silver ions by the PPy film took place and silver particles were adsorbed onto the film surface. The silver particles content at the PPy films were analyzed by QCM and the results showed that the concentrations of silver uptakes increase as the original AgNO₃ solution increases. The morphology of the surface of the PPy film and the silver-PPy film composite were studied by the scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectrometry (EDX). They showed that the obtained silver particles have spherical, cubic and tetrahedral structures. X-ray diffraction (XRD) and Fourier transformed infra-red spectroscopy (FTIR) were used to characterize the structure of the powder composite. This work reveals the capability of PPy film coating on QCM in sensing and removing silver from several environmental samples.     

纳米银导电膜的制备及其光谱学分析

为了以温和的化学反应制备纳米银导电膜,在PET薄膜上涂布柠檬酸银乳液,并用抗坏血酸(Vc)还原,用红外光谱仪、紫外-可见光分光光度计、X射线衍射仪(XRD)、扫描电子显微镜、原子力显微镜等,研究柠檬酸银乳液及其还原涂层的微观形貌、晶体结构和导电性能。发现PVP保护的柠檬酸银乳液粒径分布在60～150 nm。银膜的UV-Vis吸收峰位于430 nm,表明其具有纳米结构。XRD分析表明,还原后的涂层形成了不完整的银晶体,水洗比乙醇处理更能促进柠檬酸银的彻底还原和银膜的晶型完善,降低银膜表面电阻。     

Development and evaluation of electroless Ag-PTFE composite coatings with anti-microbial and anti-corrosion properties

Electroless Ag-polytetrafluoroethylene (PTFE) composite coatings were prepared on stainless steel sheets. The existence and distribution of PTFE in the coatings were analysed with an energy dispersive X-ray microanalysis (EDX). The contact angle values and surface energies of the Ag-PTFE coatings, silver coating, stainless steel, titanium and E. coli Rosetta were measured. The experimental results showed that stainless steel surfaces coated with Ag-PTFE reduced E. coli attachment by 94-98%, compared with silver coating, stainless steel or titanium surfaces. The anti-bacterial mechanism of the Ag-PTFE composite coatings was explained with the extended Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. The anticorrosion properties of the Ag-PTFE composite coatings in 0.9% NaCl solution were studied. The results showed that the corrosion resistance of the Ag-PTFE composite coatings was superior to that of stainless steel 316L.     

Enhanced photocatalytic activity of TiO2 nano-structured thin film with a silver hierarchical configuration

TiO₂ sol-gels with various Ag/TiO₂ molar ratios from 0 to 0.9% were used to fabricate silver-modified nano-structured TiO₂ thin films using a layer-by-layer dip-coating (LLDC) technique. This technique allows obtaining TiO₂ nano-structured thin films with a silver hierarchical configuration. The coating of pure TiO₂ sol-gel and Ag-modified sol-gel was marked as T and A, respectively. According to the coating order and the nature of the TiO₂ sol-gel, four types of the TiO₂ thin films were constructed, and marked as AT (bottom layer was Ag modified, surface layer was pure TiO₂), TA (bottom layer was pure TiO₂, surface layer was Ag modified), TT (pure TiO₂ thin film) and AA (TiO₂ thin film was uniformly Ag modified). These thin films were characterized by means of linear sweep voltammetry (LSV), X-ray diffraction (XRD), scanning electron microscopy (SEM), electrochemical impedance spectroscopy and transient photocurrent (I_ph). LSV confirmed the existence of Ag⁰ state in the TiO₂ thin film. SEM and XRD experiments indicated that the sizes of the TiO₂ nanoparticles of the resulting films were in the order of TT > AT > TA > AA, suggesting the gradient Ag distribution in the films. The SEM and XRD results also confirmed that Ag had an inhibition effect on the size growth of anatase nanoparticles. Photocatalytic activities of the resulting thin films were also evaluated in the photocatalytic degradation process of methyl orange. The preliminary results demonstrated the sequence of the photocatalytic activity of the resulting films was AT > TA > AA > TT. This suggested that the silver hierarchical configuration can be used to improve the photocatalytic activity of TiO₂ thin film.     

Effects of metal doping on the physical properties of ZnTe thin films

Zinc telluride (ZnTe) thin films were sublimated on a glass substrate using closed space sublimation (CSS) technique. ZnTe thin films of same thickness were tailored with copper (Cu) & silver (Ag) doping, considered for comparative study. X-ray diffraction (XRD) patterns of as-deposited ZnTe thin film and doped ZnTe samples exhibited polycrystalline behavior. The preferred orientation of (111) having cubic phase was observed. XRD patterns indicated that the crystallite size had increased after silver and copper immersion in as-deposited ZnTe thin films. Scanning electron microscopy (SEM) was used to observe the change of as-deposited and doped sample's grains sizes. EDX confirmed the presence of Cu and Ag in the ZnTe thin films after doping respectively. The optical studies showed the decreasing trend in energy band gap after Cu and Ag-doping. Transmission also decreased after doping. Resistivity of as-deposited ZnTe thin film was about 10⁶ Ω cm. The resistivity was reduced to 68.97 Ω cm after Cu immersion, and 10⁴ Ω cm after Ag immersion. Raman spectra were used to check the crystallinity of as-deposited, Cu and Ag-doped ZnTe thin film samples.     

Ultrasonic, chemical stability and preparation of self-assembled fullerene[C60]-gold nanoparticle films

C(60)-functionalized gold nanoparticle films were self-assembled on the reactive surface of glass slides functionalized with 3-aminopropyltrimethoxysilane. The functionalized glass slides were alternately soaked in the solutions containing unmodified C(60) and 4-aminothiophenoxide/hexane thiolate-protected gold nanoparticles. Organic reaction (amination) facilitated the layer-by-layer multilayer film assembly. C(60)-functionalized gold nanoparticle films have grown up to several layers (upto 5 layers were examined) depending on the immersion time. The assembled nanoparticle films were characterized using UV-vis spectroscopy. The chemical stability of C(60)-gold nanoparticle films was studied by monitoring the changes in absorbance after the immersion of the films in acidic solutions. The ultrasonic stability of these nanoparticle films was studied by exposing them to ultrasonic irradiated surrounding, which results in the aggregation of nanoparticles on solid surfaces.     

Investigation of ageing effects on the electrical properties of polyaniline/silver nanocomposites

Polyaniline(PANI)/Ag nanocomposites, synthesized by incorporation of separately prepared silver nanoparticles in 1-methyl-2-pyrrolidinone(NMP) solution of PANI, have been aged at the accelerated temperature of 120 oC to simulate a storage period of 2 years at 25 oC. The accelerated ageing of these materials is done by using the activation energy calculated from data collected using heat flow calorimetry (HFC). The impedance spectroscopic studies of NMP plasticized aged nanocomposite films suggest a microphase separation into reduced and oxidized repeat units. There is crosslinking of the PANI films during ageing thereby obstructing the charge transfer between PANI chains and silver nanoparticles. As a result, the resistivity is increased.     

Preparation of superhydrophobic films on titanium as effective corrosion barriers

Stable superhydrophobic films were prepared on the electrochemical oxidized titania/titanium substrate by a simple immersion technique into a methanol solution of hydrolyzed 1H,1H,2H,2H-perfluorooctyltriethoxysilane [CF₃(CF₂)₅(CH₂)₂Si(OCH₂CH₃)₃, PTES] for 1 h at room temperature followed by a short annealing at 140 °C in air for 1 h. The surface morphologies and chemical composition of the film were characterized by means of water contact angle (CA), field emission scanning electron microscopy (FESEM), atomic force microscope (AFM) and X-ray photoelectron spectroscopy (XPS). The water contact angle on the surface of this film was measured to be as high as 160°. SEM images showed that the resulting surfaces exhibited special hierarchical structure. The special hierarchical structure along with the low surface energy leads to the high surface superhydrophobicity. The corrosion resistance ability and durance property of the superhydrophobic film in 3.5 wt.% NaCl solution was evaluated by the electrochemical impedance spectroscopy (EIS). The anticorrosion properties of the superhydrophobic film are compared to those of unmodified pure titanium and titania/titanium substrates. The results showed that the superhydrophobic film provides an effective corrosion resistant coating for the titanium metal even with immersion periods up to 90 d in the 3.5 wt.% NaCl solution, pointing to promising future applications.     

Biocompatible polymeric implants for controlled drug delivery produced by MAPLE

Implants consisting of drug cores coated with polymeric films were developed for delivering drugs in a controlled manner. The polymeric films were produced using matrix assisted pulsed laser evaporation (MAPLE) and consist of poly(lactide-co-glycolide) (PLGA), used individually as well as blended with polyethylene glycol (PEG). Indomethacin (INC) was used as model drug. The implants were tested in vitro (i.e. in conditions similar with those encountered inside the body), for predicting their behavior after implantation at the site of action. To this end, they were immersed in physiological media (i.e. phosphate buffered saline PBS pH 7.4 and blood). At various intervals of PBS immersion (and respectively in blood), the polymeric films coating the drug cores were studied in terms of morphology, chemistry, wettability and blood compatibility. PEG:PLGA film exhibited superior properties as compared to PLGA film, the corresponding implant being thus more suitable for internal use in the human body. In addition, the implant containing PEG:PLGA film provided an efficient and sustained release of the drug. The kinetics of the drug release was consistent with a diffusion mediated mechanism (as revealed by fitting the data with Higuchi's model); the drug was gradually released through the pores formed during PBS immersion. In contrast, the implant containing PLGA film showed poor drug delivery rates and mechanical failure. In this case, fitting the data with Hixson-Crowell model indicated a release mechanism dominated by polymer erosion.     

ESCA-studies of the structure and composition of the passive film formed on stainless steels by various immersion times in 0.1 M NaCl solution

This report deals with the structure of the passive film formed on stainless steels during immersion in a 0.1 M NaCl solution for various immersion times. The film was examined using ion etching and Electron Spectroscopy for Chemical Analysis (ESCA).Through the chemical-composition profiles a three-factor model was developed to describe the structure of the passive films: a hydrated layer in contact with the solution, an oxide layer consisting of iron and chromium oxides having maxima at depths of 3 and 10 Å, respectively, and a metallic layer enriched in nickel. There is a smooth transition between the layers, with the thickness of the outer two layers being about 15 A. The maximum concentration of iron in the oxidized state decreases with increasing immersion time concomitant with an increase in both the maximum concentration of chromium in the oxidized state and the maximum concentration of nickel in the metallic state.It is found that air-formed films have similar structures to films formed by exposure to the solution. Longer air exposure thickens the air-formed film, with the maximum of both oxidized iron and chromium nearly equal in magnitude in comparison with the solution formed films. Films formed by short-time exposure only to the solution are somewhat thinner indicating that the total history is important in determining the structure of these passive films, whereas passive films formed by exposures of 15 h to the solution are no longer strongly dependent on prior air exposure.     

硬脂酸单分子膜上电沉积Ag膜的研究

通过电沉积方法 ,以气 /液界面上形成的硬脂酸单分子膜为模板诱导沉积金属银膜 .考察了镀液 pH值、单分子膜表面压及沉积电位对银膜形貌及结构的影响 .实验发现 ,酸性镀液的气 /液界面上形成的单分子膜不能诱导沉积银 ,而在中性和碱性镀液的气 /液界面上可以诱导银膜的生长 .当单分子膜处于液态或固态时 ,气 /液界面有银膜形成 ;液态单分子膜上的银膜生长速度较快 ,且银膜的结构一致 .随着电极电位的升高 ,银膜沉积的速度加快 ,呈环状向外生长的圆形银膜逐渐变得不规则 .将不同实验条件下的银膜转移出来 ,采用扫描电镜 (SEM )、透射电镜 (TEM )对银膜的结构与形貌进行了表征 .研究表明 ,银首先在单分子膜上异相成核 ,由八面体构型逐渐发展成星型 ,最终在气 /液界面形成具有松枝状微观结构的光亮银膜 .