Free-standing alumina nanobottles and nanotubes pre-integrated into nanoporous alumina membranes

A novel interfacial structure consisting of long (up to 5 μm), thin (about 300 nm), highly-ordered, free-standing, highly-reproducible aluminum oxide nanobottles and long tubular nanocapsules attached to a rigid, thin (less than 1 μm) nanoporous anodic alumina membrane is fabricated by simple, fast, catalyst-free, environmentally friendly voltage-pulse anodization. A growth mechanism is proposed based on the formation of straight channels in alumina membrane by anodization, followed by neck formation due to a sophisticated voltage control during the process. This process can be used for the fabrication of alumina nanocontainers with highly controllable geometrical size and volume, vitally important for various applications such as material and energy storage, targeted drug and diagnostic agent delivery, controlled drug and active agent release, gene and biomolecule reservoirs, micro-biologically protected platforms, nano-bioreactors, tissue engineering and hydrogen storage.     

Studies of self-organization processes in nanoporous alumina membranes by small-angle neutron scattering

We performed studies of the self-organization processes in nanoporous alumina membranes at initial and late stages of aluminum anodization by using scanning electron microscopy (SEM) and small-angle neutron scattering (SANS). SEM observations indicated three stages in the self-organization of nanopores in alumina: (1) nucleation of random nanopores with a broad radius distribution, (2) narrowing the radius distribution and (3) slow evolution of the nanoporous structure towards ordering of nanopores into large domains. SANS studies revealed orientational correlation between ordered domains of nanopores, which is characterized by a small misorientation angle. For the samples with high aspect ratios of nanopores, the SANS patterns showed azimuthal smearing, which was attributed to the redistribution of nanopores between the domains during their growth.     

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.     

Surface modification processes by hypervelocity plasma pulses

The Institute of Astronautics of the Technische Universität München works in the field of electrothermal and electromagnetic particle launchers. Capacitor-driven arc discharges generated within these accelerators eject very fast and dense plasma pulses that can be used to modify surfaces of metals and alloys. During the last years, a completely new facility for surface modification purposes was designed, built, and put into operation. In preparation for the industrial application of the plasma-pulse-technique, further modifications and optimizations of the facility were performed. Fast and reliable feeding of seeding and/or reaction products to the plasma was realized with a specially designed and built gas injection system. Very short opening times for the injection valves could be realized. It is now possible to supply a substantial amount of gas to the process. The pressure pulse from the gas injection allows uniformly and finely distributed feeding of pulverized additives to the plasma as well. For the first time, we generated a carbon–nickel plasma that was used for steel-hardening. In contrast to our former experiments, a hard surface but largely free of fissures could be generated. This is a necessary and important step towards an industrial application of the plasma-pulse-technique. A different application is the surface doping of titanium aluminides (TiAl) with chlorine atoms. This modification leads to a substantial reduction of the oxidation of such materials. This is essential for the high temperature regime of turbine blades in jet engines. After the modification of the gas injection system for chlorine, TiAl samples were impacted with chlorine doped plasma pulses and the oxidation was tested. A reduced oxidation was observed which proves the principle applicability of the plasma pulse process for this special application.     

Nondestructive replication of self-ordered nanoporous alumina membranes via cross-linked polyacrylate nanofiber arrays

Ordered nanofiber arrays are a promising material platform for artificial adhesive structures, tissue engineering, wound dressing, sensor arrays, and self-cleaning surfaces. Their production via self-ordered porous alumina hard templates serving as shape-defining molds is well-established. However, their release requires the destruction of the hard templates, the fabrication of which is costly and time-consuming, by wet-chemical etching steps with acids or bases. We report the nondestructive mechanical extraction of arrays of cross-linked polyacrylate nanofibers from thus recyclable self-ordered nanoporous alumina hard templates. Silica replicas of the latter were synthesized using the extricated nanofiber arrays as secondary molds that could be mechanically detached from the molded material. The approach reported here, which can be combined with microstructuring, may pave the way for the high-throughput production of both functional nanofiber arrays and ordered nanoporous membranes consisting of a broad range of material systems.     

甲基丙烯酸甲酯对纳米SiO2的表面接枝聚合改性研究

将经过硅烷化处理的偶联剂γ-MPS接枝到纳米SiO2表面,然后在引发剂AIBN的作用下引发单体MMA发生自由基聚合包覆.利用FTIR、TG、CA(接触角)以及TEM等手段分别表征了改性工艺条件对粒子改性前后化学组成结构、接枝率、表面亲水性以及形貌等的影响.系统研究了单体用量、引发剂用量以及反应时间对SiO2/γ-MPS/PM-MA纳米复合粒子接枝改性效果的影响.结果表明,经过PMMA接枝包覆制得了高接枝率的复合粒子,并大大改善了纳米粒子的分散性.     

Fabrication of metallic nanowire arrays by electrodeposition into nanoporous alumina membranes: effect of barrier layer

Deposition into nanoporous alumina membranes is widely used for nanowire fabrication. Herein using AC electrodeposition ternary Fe–Co–Ni nanowires are fabricated within the nanoscale-pores of alumina membranes. Using an electrodeposition frequency of 1,000 Hz, 15 V_rms, consistently and repeatably yield nanowire arrays over membranes several cm² in extent. Electrochemical Impedance Spectroscopy (EIS) is used to explain the effects of AC electrodeposition frequency. The impedance of the residual alumina barrier layer, separating the underlying aluminum metal and the nanoporous membrane, decreases drastically with electrodeposition frequency facilitating uniform pore-filling of samples several cm² in area. Anodic polarization studies on thin films having alloy compositions identical to the nanowires display excellent corrosion resistance properties.     

Surface modification of poly(ethylene terephthalate) by plasma polymerization of poly(ethylene glycol)

Poly(ethylene glycol) (PEG) was ‘polymerized’ onto poly(ethylene terephthalate) (PET) surface by radio frequency (RF) plasma polymerization of PEG (average molecular weight 200 Da) at a monomer vapour partial pressure of 10 Pa. Thin films strongly adherent onto PET could be produced by this method. The modified surface was characterized by infra red (IR) spectroscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), cross-cut test, contact angle measurements and static platelet adhesion studies. The modified surface, believed to be extensively cross-linked, however showed all the chemical characteristics of PEG. The surface was found to be highly hydrophilic as evidenced by an interfacial free energy of about 0.7 dynes/cm. AFM studies showed that the surface of the modified PET became smooth by the plasma polymerized deposition. Static platelet adhesion studies using platelet rich plasma (PRP) showed considerably reduced adhesion of platelets onto the modified surface by SEM. Plasma ‘polymerization’ of a polymer such as PEG onto substrates may be a novel and interesting strategy to prepare PEG-like surfaces on a variety of substrates since the technique allows the formation of thin, pin-hole free, strongly adherent films on a variety of substrates.     

Oxygen plasma modification of polyurethane membranes

Polyurethane membranes were prepared under nitrogen atmosphere by using various proportions of toluene diisocyanates (TDI) and polypropylene-ethylene glycol (P) with addition of no other ingredients such as catalysts, initiator or solvent in order to achieve medical purity. Effects of composition on mechanical properties were examined. In general, modulus and UTS values demonstrated an increase and PSBR demonstrated a decrease as the TDI/Polyol ratio of the polymer increased. Elastic modulus, ultimate tensile strength (UTS) and per cent strain before rupture (PSBR) values were found to be in the range of 1.4–5.4 MPa, 0.9–1.9 MPa, and 60.4–99.7%, respectively. Surfaces of the membranes were modified by oxygen plasma applying glow-discharge technique and the effect of applied plasma power (10 W or 100 W, 15 min) on surface hydrophilicity and on the attachment of Vero cells were studied. Water contact angle values of the plasma modified surfaces varied between 67° and 46°, demonstrating a decrease as the applied plasma power was increased. The unmodified material had 42–45 cells attached per cm². It was observed that as the applied power increased the number of attached cells first increased (60–70 cells/cm² at 10 W) and then decreased (27–40 cells/cm² at 100 W). These demonstrated that surface properties of polyurethanes can be modified by plasma-glow discharge technique to achieve the optimum levels of cell attachment.     

Evidence for microwave enhanced mass transport in the annealing of nanoporous alumina membranes

Results of a comparative study of pore evolution in nanostructured alumina membranes under annealing in a gyrotron microwave system and in conventional furnace are described. Microwave heating has resulted in an enhanced mass transport leading to reduction in the surface porosity of the membranes. Evolution patterns for the shape of individual pores are discussed and compared for microwave and conventional annealing. The notably different behavior of the pores suggests that microwave radiation provides an additional driving force for mass transport. The experimentally observed enhancement of mass transport appears to be stronger than predicted by the earlier proposed models.     

多壁碳纳米管表面等离子体有机聚合改性

采用等离子体聚合技术在多壁碳纳米管(MWNTs) 表面聚合苯乙烯( Styrene) 、吡咯( Pyrrole) 有机膜。高分辨电镜( HRTEM) 分析显示MWNTs 内外表面均生成纳米级厚度的有机膜, 其中外壁表面厚约7 nm , 内壁表面厚约1～3 nm。将经过表面有机膜处理的MWNTs 添加到聚苯乙烯中, 制备出多壁碳纳米管/ 聚苯乙烯(MWNTs/ PS) 复合材料。扫描电镜(SEM) 对MWNTs/ PS 复合材料分析表明, 覆膜的MWNT 在复合材料中的分散得到改善。通过力学拉伸试验测试了MWNTs/ PS 复合材料断裂强度和弹性模量与MWNTs 含量的关系, 证明了经有机覆膜处理的MWNTs 与PS 形成的复合材料的整体强度得到显著提高。      

聚丙烯微孔膜表面接枝聚合丙烯酰胺的改性研究

用化学方法在聚丙烯微孔膜表面接枝丙烯酰胺单体,分别考察了反应温度、单体浓度、反应时间和引发剂浓度等反应因素对接枝率的影响,红外光谱和扫描电镜证实了丙烯酰胺在聚丙烯微孔膜表面的接枝,水接触角测试显示接枝膜具有良好的亲水性,热分析表明接枝膜基本没有改变聚丙烯微孔膜的基体性质.实验发现当反应温度为60℃,单体浓度为10%,反应时间为4h,引发剂浓度为2.0×10-3mol/L时,获得最佳接枝效果.     

Preparation of gas separation membranes by plasma polymerization with fluoro compounds

Plasma polymerization coatings were applied for the preparation of gas separation membranes. Mainly fluoro compounds were used as coating materials. The membranes showed good separation characteristics with high flux for gaseous systems. The plasma polymerization composite parameter given by W/FM plays an important role in obtaining excellent separation characteristics. The correlation between the conversion rate DR/FM, where DR is the deposition rate of plasma polymer, and W/FM is useful to consider the plasma polymer character under the different plasma polymerization conditions (discharge power W and monomer flow rate F). The proper conditions for membrane preparation lie in the intermediate region between the region in which the monomer flow rate is deficient and that in which the discharge power is deficient. Furthermore, the plasma polymerization coatings with the higher molecular weight monomer gave the higher separation characteristics. Plasma polymer composite membranes in this study showed superiority for the molecular sieve type of separation over the solution-diffusion type of separation.     

Surface modification of nano-SiO2 by in situ grafted polymerization of butyl methacrylate

Silane coupling agent was used to introduce polymeric groups that was C=C onto the surface of nano-SiO₂ particles by self-assembling technique. Then, in situ grafted polymerization was carried out between the functionalized particles and butyl methacrylate monomers under the action of an initiating agent to accomplish the surface modification of nano-SiO₂. The effect of different reaction conditions on grafting percentage was studied, and analyses of FTIR, TEM, and TG-DTA results show that new organic chains were introduced onto the surface of nano-SiO₂, and the dispersion stability of nano-SiO₂ in THF was obviously improved. The text was submitted by the authors in English.