Fabrication of Cu nano-arrays by template method and their characterizations

Cu nanotubes and nanowires were fabricated by electroless deposition using porous aluminum oxide membrane as template in coating bath at room temperature. The images of Cu nanotubes and nanowires are obtained by transmission electron microscopy (TEM). X-ray diffractometry (XRD) is employed to study the morphology. Results indicate that the success of fabrication depends on the reducing process of pore treatment. The outer diameter of Cu nanotubes can be controlled by adjusting the aperture of anodic alumina membranes (AAM) template, and the thickness of the tube wall can be controlled by deposition time. The morphology of Cu nanotubes and nanowires are polycrystalline. Translated from Metallic Functional Materials, 2006, 13(5): 1–4 (in Chinese)     

Surface properties of thin gold layers sputtered on polymers

Thin gold layers were sputtered on the foils of polypropylene-PP, polyethyleneterephthalate-PET, polystyrene-PS, polyethylene-PE and polytetrafluoroethylene-PTFE modified by Ar+ plasma. Surface properties of pristine, plasma treated and gold coated polymers were characterized by two-points method (sheet electrical resistance), electrokinetical analysis (zeta-potential, surface chemistry), goniometry (contact angle), electron paramagnetic resonance (concentration of radicals), atomic force microscopy (AFM, surface morphology and roughness) and scratch test (mechanical properties). Zeta potential and contact angle, as assumed, differ dramatically for plasma treated polymers and for the polymers deposited by Au layers. AFM images indicate that after gold deposition on polymers the surface roughness and the surface morphology change depending on pristine polymer surfaces (roughness and morphology) and sputtering time. Electrical measurements resulted in fact that with increasing layer thickness, the sheet resistance of the gold layer decreases for all polymers with increasing sputtering time. Lower adhesive destruction is observed on the gold layer deposited on plasma treated PE in comparison with pristine.     

Structure-dependent adhesion and friction on highly ordered metallic nanopore membranes

Highly ordered metallic nanopore membranes are fabricated by direct deposition of nickel on typical porous anodic alumina (PAA) templates. The large-area uniform nanopore arrays of the PAA templates are accurately transferred to the metallic nanopore replicas, depending on the thickness of the deposited metal and the pore size of the base template. We demonstrate the ready tunability of the pore size and reproducibility of the metallic nanopore structure in a wide range of pore sizes. The adhesion and friction characteristics of the metallic replicas are studied according to the pore size using atomic force microscopy (AFM). As the pore diameter increases, the friction coefficients increase nonlinearly, and the adhesive forces scarcely change. These characteristics are understood in terms of the structural properties of the replicas, specifically the surface morphology and the real contact area. Initial pore formation from a flat thin film reduces the adhesive force by up to four times.     

Plasma modification of polyacrylonitrile ultrafiltration membrane

Polyacrylonitrile (PAN) ultrafiltration (UF) membranes were modified by plasma treatments and plasma polymerization. Influences of plasma modifications on membrane characteristics were investigated. The obtained results indicated that plasma treatments using non-polymer-forming plasma gases such as Ar, He and O₂ led to the increase of membrane surface hydrophilicity and membrane permeability. By using O₂ plasma treatment, UF property of PAN membranes could be improved with the enhancement of membrane flux meanwhile its albumin rejection was almost maintained. The experimental results also showed that plasma polymerization using acrylic acid vapor as monomer and PAN UF membrane as a substrate led to the formation of reverse osmosis membrane due to the deposition of plasma polymer layer onto substrate membrane surfaces. Plasma techniques can control membrane pore size and have a potential to improve the membrane characteristics by using their advantages.     

低温等离子体接枝改性PVDF膜

采用低温等离子体接枝技术改性聚偏氟乙烯膜(PVDF),在PVDF膜表面引入疏水性单体苯乙烯,达到改变膜表面孔径的大小和孔径分布的目的.通过傅立叶红外光谱仪(FTIR-ATR)对改性前后的PVDF膜表面进行了结构分析,考察了PVDF膜接枝前后官能团的变化.采用示差扫描量热仪(DSC)分析了PVDF改性前后膜的孔径分布,考察了改性条件对膜孔径大小和分布的影响.通过扫描电子显微镜(SEM)和原子力显微镜(AFM)观测了PVDF膜改性前后表面形貌的变化.研究了接枝温度、接枝时间等接枝条件对PVDF改性膜纯水通量的影响.结果表明,随着照射时间和接枝时间的延长,PVDF改性膜的孔径分布变窄,纯水通量下降,接枝率提高.     

ATRP-based synthesis and characterization of light-responsive coatings for transdermal delivery systems

Abstract

The grafting of poly(hydroxyethylmethacrylate) on polymeric porous membranes via atom transfer radical polymerization (ATRP) and subsequent modification with a photo-responsive spiropyran derivative is described. This method leads to photo-responsive membranes with desirable properties such as light-controlled permeability changes, exceptional photo-stability and repeatability of the photo-responsive switching. Conventional track etched polyester membranes were first treated with plasma polymer coating introducing anchoring groups, which allowed the attachment of ATRP-initiator molecules on the membrane surface. Surface initiated ARGET–ATRP of hydroxyethylmethacrylate (where ARGET stands for activator regenerated by electron transfer) leads to a membrane covered with a polymer layer, whereas the controlled polymerization procedure allows good control over the thickness of the polymer layer in respect to the polymerization conditions. Therefore, the final permeability of the membranes could be tailored by choice of pore diameter of the initial membranes, applied monomer concentration or polymerization time. Moreover a remarkable switch in permeability (more than 1000%) upon irradiation with UV-light could be achieved. These properties enable possible applications in the field of transdermal drug delivery, filtration, or sensing.     

ATRP-based synthesis and characterization of light-responsive coatings for transdermal delivery systems

The grafting of poly(hydroxyethylmethacrylate) on polymeric porous membranes via atom transfer radical polymerization (ATRP) and subsequent modification with a photo-responsive spiropyran derivative is described. This method leads to photo-responsive membranes with desirable properties such as light-controlled permeability changes, exceptional photo-stability and repeatability of the photo-responsive switching. Conventional track etched polyester membranes were first treated with plasma polymer coating introducing anchoring groups, which allowed the attachment of ATRP-initiator molecules on the membrane surface. Surface initiated ARGET–ATRP of hydroxyethylmethacrylate (where ARGET stands for activator regenerated by electron transfer) leads to a membrane covered with a polymer layer, whereas the controlled polymerization procedure allows good control over the thickness of the polymer layer in respect to the polymerization conditions. Therefore, the final permeability of the membranes could be tailored by choice of pore diameter of the initial membranes, applied monomer concentration or polymerization time. Moreover a remarkable switch in permeability (more than 1000%) upon irradiation with UV-light could be achieved. These properties enable possible applications in the field of transdermal drug delivery, filtration, or sensing.     

Thermally controlled permeation of ionic molecules through synthetic nanopores functionalized with amine-terminated polymer brushes

We present temperature-dependent ionic transport through an array of nanopores (cylindrical and conical) and a single conical nanopore functionalized with amine-terminated poly(N-isopropylacrylamide) [PNIPAAM-NH(2)] brushes. For this purpose, nanopores are fabricated in heavy ion irradiated polyethylene terephthlate (PET) membranes by a controlled chemical track-etching technique, which leads to the generation of carboxyl (COOH) groups on the pore surface. End-functionalized polymer chains are immobilized onto the inner pore walls via a 'grafting-to' approach through the covalent linkage of surface COOH moieties with the terminal amine groups of the PNIPAAM molecules by using carbodiimide coupling chemistry. The success of the chemical modification reaction is corroborated by measuring the permeation flux of charged analytes across the multipore membranes in an aqueous solution, and for the case of single conical pore by measuring the current-voltage (I-V) characteristics, which are dictated by the electrostatic interaction of the charged pore surface with the mobile ions in an electrolyte solution. The effective nanopore diameter is tuned by manipulating the environmental temperature due to the swelling/shrinking behaviour of polymer brushes attached to the inner nanopore walls, leading to a decrease/increase in the ionic transport across the membrane. This process should permit the thermal gating and controlled release of ionic drug molecules through the nanopores modified with thermoresponsive polymer chains across the membrane.     

Pulsed plasma polymerization for controlling shrinkage and surface composition of nanopores

Solid-state nanopores have emerged as sensors for single molecules and these have been employed to examine the biophysical properties of an increasingly large variety of biomolecules. Herein we describe a novel and facile approach to precisely adjust the pore size, while simultaneously controlling the surface chemical composition of the solid-state nanopores. Specifically, nanopores fabricated using standard ion beam technology are shrunk to the requisite molecular dimensions via the deposition of highly conformal pulsed plasma generated thin polymeric films. The plasma treatment process provides accurate control of the pore size as the conformal film deposition depends linearly on the deposition time. Simultaneously, the pore and channel chemical compositions are controlled by appropriate selection of the gaseous monomer and plasma conditions employed in the deposition of the polymer films. The controlled pore shrinkage is characterized with high resolution AFM, and the film chemistry of the plasma generated polymers is analyzed with FTIR and XPS. The stability and practical utility of this new approach is demonstrated by successful single molecule sensing of double-stranded DNA. The process offers a viable new advance in the fabrication of tailored nanopores, in terms of both the pore size and surface composition, for usage in a wide range of emerging applications.     

Orthogonal functionalization of nanoporous substrates: control of 3D surface functionality

Anodic aluminum oxide (AAO) membranes with aligned, cylindrical, nonintersecting pores were selectively functionalized in order to create dual-functionality substrates with different pore-rim and pore-interior surface functionalities, using silane chemistry. We used a two-step process involving an evaporated thin gold film to protect the underlying surface functionality of the pore rims. Subsequent treatment with oxygen plasma of the modified AAO membrane removed the unprotected organic functional groups, i.e., the pore-interior surface. After gold removal, the substrate became optically transparent, and displayed two distinct surface functionalities, one at the pore-rim surface and another at the pore-interior surface. We achieved a selective hydrophobic functionalization with dodecyl-trichlorosilane of either the pore rims or the pore interiors. The deposition of planar lipid membranes on the functionalized areas by addition of small unilamellar vesicles occurred in a predetermined fashion. Small unilamellar vesicles only ruptured upon contact with the hydrophobic substrate regions forming solid supported hybrid bilayers. In addition, pore-rim functionalization with dodecyl-trichlorosilane allowed the formation of pore-spanning hybrid lipid membranes as a result of giant unilamellar vesicle rupture. Confocal laser scanning microscopy was employed to identify the selective spatial localization of the adsorbed fluorescently labeled lipids. The corresponding increase in the AAO refractive index due to lipid adsorption on the hydrophobic regions was monitored by optical waveguide spectroscopy. This simple orthogonal functionalization route is a promising method to control the three-dimensional surface functionality of nanoporous films.     

Increased response of Vero cells to PHBV matrices treated by plasma

The copolymers poly(3-hydroxybutyric acid-co-3-hydroxyvaleric acid) (PHBV) are being intensely studied as a tissue engineering substrate. It is known that poly 3-hydroxybutyric acids (PHBs) and their copolymers are quite hydrophobic polyesters. Plasma-surface modification is an effective and economical surface treatment technique for many materials and of growing interest in biomedical engineering. In this study we investigate the advantages of oxygen and nitrogen plasma treatment to modify the PHBV surface to enable the acceleration of Vero cell adhesion and proliferation. PHBV was dissolved in methylene chloride at room temperature. The PHBV membranes were modified by oxygen or nitrogen-plasma treatments using a plasma generator. The membranes were sterilized by UV irradiation for 30 min and placed in 96-well plates. Vero cells were seeded onto the membranes and their proliferation onto the matrices was also determined by cytotoxicity and cell adhesion assay. After 2, 24, 48 and 120 h of incubation, growth of fibroblasts on matrices was observed by scanning electron microscopy (SEM). The analyses of the membranes indicated that the plasma treatment decreased the contact angle and increased the surface roughness; it also changed surface morphology, and consequently, enhanced the hydrophilic behavior of PHBV polymers. SEM analysis of Vero cells adhered to PHBV treated by plasma showed that the modified surface had allowed better cell attachment, spreading and growth than the untreated membrane. This combination of surface treatment and polymer chemistry is a valuable guide to prepare an appropriate surface for tissue engineering application.     

静电纺丝制备多孔醋酸纤维素超细纤维

采用静电纺丝法制备了大量尺寸为60 nm～750 nm椭圆形多孔醋酸纤维素(CA)纤维.利用扫描电镜(SEM)表征了纤维及孔的形态和大小,液氮吸附法(BET)测定了纤维的比表面积.探讨了溶刑种类、溶剂配比和溶液浓度对多孔CA纤维的影响.通过调节纺丝溶液性质和纺丝参数,CA纤维表面多孔大小和分布密度是可调控的.成孔机理是...     

Surface-enhanced Raman spectroscopy of the growth of ultra-thin organosilicon plasma polymers on nanoporous Ag/SiO2-bilayer films

A new method for the synthesis of thin bilayer films as surface-enhanced Raman spectroscopy (SERS) active substrates was developed which is based on the combination of plasma polymerization, plasma calcination and Ag-film deposition by means of physical vapor deposition. The surface morphology of prepared substrates was characterized by field emission scanning electron microscopy, atomic force microscopy and electrochemical impedance spectroscopy. These substrates lead to high surface enhancement factors proven by the spectroscopic analysis of adsorbed Trans-1,2 bis-(4-pyridyl) ethylene molecules. By this preparation technique, SERS-active films can be deposited on any substrate. The new SERS substrates were successfully applied to study the growth of ultra-thin hexamethyldisiloxane plasma polymer films. The Raman intensity of the CH-stretching vibration was studied as a function of the film thickness. The surface enhancement decreased sharply at about 20 nm. The resulting increase in the intensity of Raman peaks for thin adsorbed plasma polymer films was observed to be a combination of the electromagnetic enhancement mechanism and the high surface area increase of the rough Ag-surface.     

Hydrocarbon decomposition in alumina membrane: an effective way to produce carbon nanotubes bundles

Carbon nanotubes were synthesised within the pores of an alumina membrane. The membrane had 200 nm diameter pores and 60 microm thickness, and ethylene was used as carbon source. Membrane dissolution by HF results in a bundle of parallel open tubes, aligned without macroscopic defects. The external diameter of the tubes is uniform and there is no evidence of any amorphous carbon. Wall thickness control was obtained by varying the reaction time, length by the thickness of alumina membrane, and external tube diameter by the membrane pore size. Scanning (SEM) and transmission (TEM) electron microscopy, atomic force microscopy (AFM), X-ray diffraction, thermogravimetric analysis (TG) and surface area evaluation by nitrogen adsorption were used for the characterization of membrane and nanotubes.     

Asymmetric Membranes Based on Fullerene‐Containing Polyphenylene Oxide

Abstract

Fullerene‐containing polyphenylene oxide (C₆₀–PPO) asymmetric membranes were prepared by phase inversion technique and compared with PPO asymmetric membranes. To study membrane morphology, atomic force microscopy (AFM) and scanning electron microscopy (SEM) were used. Scanning electron microscopy made it possible to resolve the structure of skin surface and cross‐section and also to estimate membrane porosity and pore size. For dynamic characterization, the membranes were tested for permeability and rejection of seven proteins with different molecular weights in an aqueous solution. It was established that fullerene as a component of the C₆₀–PPO mixed matrix polymer system profoundly affects the porous structure formation and the membrane properties.     

直流碳弧法制备碳包覆铁纳米颗粒机理研究

采用直流碳弧等离子体法成功制备了碳包覆铁纳米颗粒,利用透射电子显微镜和高分辨透射电子显微镜、X射线衍射、X射线能谱仪对样品的形貌、物相结构、化学成分和粒度进行表征分析,并对碳包覆纳米金属颗粒的形成机理进行初步探讨。结果表明:直流碳弧等离子体技术制备的碳包覆纳米金属颗粒具有明显的铁核(bcc-Fe)/碳壳(石墨层片)包覆结构,颗粒大多呈球形和椭球形,粒径分布在20~60nm范围,平均粒径为44nm,铁粒子外碳层的厚度为5~8nm。碳包覆铁纳米铁颗粒是通过颗粒内部固态形式的碳自行扩散至颗粒表面和颗粒外部气态形式的碳沉积到颗粒表面形成的。     

聚砜-Fe3O4磁性复合超滤膜截留分子量随磁场的变化规律

在制备聚砜-Fe3O4磁性复合超滤膜的过程中,为避免纳米Fe3O4粒子团聚,采用偶联剂包裹共沉淀法得到Fe3O4粒子,然后采用相转化法制备了聚砜-Fe3O4磁性复合超滤膜。Zeta电位仪检测出纳米粒子平均粒径为66.83 nm,红外分析发现偶联剂结合在粒子表面。经扫描电镜观察和孔径分布分析得出复合膜中纳米Fe3O4粒子分布均匀,无团聚现象出现,孔径分布较窄。聚乙二醇系列测定基膜为2万的复合膜截留分子量从0T下的19800减小至0.4T的15000,继续增大外加磁场,截留分子量基本不再变化。     

AFM and SEM characterization of iron oxide coated ceramic membranes

Alumina–zirconia–titania (AZT) ceramic membranes coated with iron oxide nanoparticles have been shown to improve water quality by significantly reducing the concentration of disinfection by-product precursors, and in the case of membrane filtration combined with ozonation, to reduce ozonation by-products such as aldehydes, ketones and ketoacids. Commercially available ceramic membranes with a nominal molecular weight cut-off of 5 kilodaltons (kD) were coated 20, 30, 40 or 45 times with sol suspension processed Fe₂O₃ nanoparticles having an average diameter of 4–6 nm. These coated membranes were sintered in air at 900 °C for 30 min. The effects of sintering and coating layer thickness on the microstructure of the ceramic membranes were characterized using atomic force microscopy (AFM), scanning electron microscopy (SEM) and energy dispersive x-ray spectroscopy (EDS). AFM images show a decreasing roughness after iron oxide coating with an average surface roughness of ∼161 nm for the uncoated and ∼130 nm for the coated membranes. SEM showed that as the coating thickness increased, the microstructure of the coating changed from a fine grained (average grain size of ∼27 nm) morphology at 20 coating layers to a coarse grained (average grain size of ∼66 nm) morphology at 40 coating layers with a corresponding increase in the average pore size from ∼57 nm to ∼120 nm. Optimum water quality was achieved at 40 layers, which corresponds to a surface coating morphology consisting of a uniform, coarse-grained structure with open, nano-sized interconnected pores.     

The Measurement of Membrane Filter Pore Size by a Gas Permeability Technique

A differential low pressure gas flow technique has been developed for the measurement of the mean pore size of membrane filters. The method is here applied to the pore size determination in a range of commercial micro-porous polymer films with pore diameters ranging from 0.03 to 0.8 μm ('Nuclepore'). The polymer films were also examined using scanning electron microscopy so that structural and physical parameters could be evaluated. Two flow regimes could be demonstrated for the permeability data with clear separation between diffusional (Knudsen) flow and viscous or transitional flow occurring at a pore size of 0.2 μm. Alternative theoretical treatments are required for the two regimes but mean pore diameters could be calculated with reasonable precision and agreed with the results obtained by microscopy. In the case of viscous flow it is necessary to assume that the membranes have a tortuosity of less than unity and this is shown to be justified from a consideration of the structure of the pore in the plastic film.     

镍纳米粉的比表面积和孔结构研究

采用阳极弧放电等离子体方法制备了高纯镍纳米粉,利用X射线衍射(XBD)、透射电子显微镜(TEM)对粉末的形貌、晶体结构、粒度进行了表征。样品的N_2的吸附-脱附等温线采用静态表面吸附仪在液氮温度下(78 K)在气体饱和蒸气压力范围内测试。依据BJH理论模型计算探讨了样品的累积孔表面积、累积孔体积、孔径及其BJH脱附分布等性能。用图解法由等温吸附直线求出单层吸附量,利用BET吸附公式计算出样品的比表面积。结果表明,镍纳米粉的比表面积为14.23 m~2/g,粒径为46 nm。