纳米氧化铝有序多孔膜制备工艺研究

为了获得大面积有序孔排列以及不同孔径的氧化铝膜,采用二次阳极氧化法可制备大面积有序铝阳极氧化多孔(AAO)膜,着重研究氧化电压、氧化时间、电解液浓度以及扩孔时间对AAO膜孔径大小、膜层厚度和形貌结构的影响,用X射线粉末衍射(XRD)仪进行物相分析,利用扫描电子显微镜(SEM)表征多孔膜的形貌.结果表明,在700 ℃以下条件下AAO膜以无定形态存在,经800 ℃退火后无定形氧化铝转化为γ-Al2O3,多孔膜随电压和电解液浓度增加而增大,经H3PO4溶液扩孔后可获得较大孔径模板,扩孔时间与孔径变化呈近似线性关系.为满足应用需求的AAO膜的制备提供了依据.     

单通氧化铝模板的制备及工艺优化

利用高纯铝片采用两步阳极氧化法制得排列高度有序、尺寸可控的单通氧化铝(anodic aluminum oxide templates,AAO)模板,且纳米孔呈六方形结构。分别探究了预处理条件、氧化次数、扩孔时间等对AAO模板尺寸及有序性的影响。结果表明,预处理利于纳米管形成高度有序结构,并发现二次阳极氧化法比一次阳极氧化法制备的纳米管排列更有序且孔径均匀;在0~75 min内,管孔径与扩孔时间呈线性关系,酸溶液对孔的腐蚀速率为0.601nm/min,在0~120min内,管长度与二次氧化时间呈线性关系,生长速率为0.28μm/min;最佳电解液浓度确定为0.3mol/L。为后续制备非对称丝岛状骨组织再生高分子薄膜奠定了良好基础。     

AAO模板快速制备方法探究

为了快速制备出高度有序且孔径可调控的AAO(阳极氧化铝)模板应用于工业生产,通过改进传统的两步阳极氧化法,采用逐步提高电解液浓度的硬氧氧化法制备了AAO模板,并确定了最佳制备工艺为初始电解液浓度0.15mol/L,添加电解液浓度0.40mol/L,温度保持在5℃左右,无水乙醇添加比例为1:1,从而使铝片的击穿电压从40V上升到130V左右(模板面积1.5cm×4.5cm),采用DimensionEdge型号的原子力显微镜(AFM)对多孔氧化铝模板进行了表征。结果表明:未经退火处理的铝片,也可以制备出高度有序的AAO模板,但其粗糙度略有增加,并与在高压条件下二次氧化、三次氧化、四次氧化制备AAO模板进行了比较,发现二次氧化制备的AAO模板有序度、孔径、孔间距均优于三次、四次氧化法。     

长程有序纳米孔氧化铝模板的制备与研究

以硫酸和草酸溶液为电解液,采用二次阳极氧化法制备出高度长程有序的纳米孔氧化铝(AAO)模板,并结合扫描电子显微镜(SEM)对其微观结构及形貌进行了观察和表征.通过研究不同的氧化电压和电解液浓度对AAO模板纳米孔形貌(孔径、孔间距、面密度和长程有序性)的影响,得到了最佳的氧化电压和电解液浓度.     

草酸/磷酸混合介质制备高质量阳极氧化铝模板

以草酸为主导酸、磷酸为辅助酸的混合介质作为电解液,采用不对称二次氧化法制备阳极氧化铝模板(AAO模板),通过调节电压、介质配比和酸的浓度等方式研究其生长机制及优化条件.利用扫描电子显微镜(SEM)和电流监测装置对得到的AAO模板进行表征,结果表明在低压(40 V)、较低浓度草酸条件下,适量掺杂磷酸可以提升模板阵列有序性、孔洞规则性及孔径;在高压(80 V)下制备出表面具有V字型结构孔洞的模板,当混合介质中主导酸和辅助酸各自适配电压与施加电压差值比为其混合体积比倒数时所制备的模板质量最优,且随电压增大V字型结构的孔径增大,但辅助酸掺杂量不宜过高.本研究可为采用多元介质制备大孔径优质AAO模板提供参考.     

阳极氧化法制备有序纳米多孔氧化铝膜的研究

利用电化学阳极氧化的方法,在草酸溶液中,精确控制反应条件,在高纯铝片表面有序生长了纳米多孔氧化铝膜。试验中,分别采用一次阳极氧化和二次阳极氧化方法制备氧化铝膜。利用H3PO4溶液浸泡法对氧化铝膜进行扩孔处理。通过扫描电子显微镜对样品进行表征分析。结果发现,二次阳极氧化制备的氧化铝膜的孔洞分布较一次氧化的更为规则有序,并且孔径大小均匀一致。扫描电镜观察显示,氧化铝膜的扩孔过程可以去掉阻碍层,并调节孔径大小,溶去二次氧化后黏附在氧化层表面的一些杂质,从而使氧化铝模板更为规则有序,孔径均一。这种经过二次阳极氧化和扩孔处理得到多孔阳极氧化铝模板的方法简单,成本较低,可以为后续的纳米材料合成提供高质量的合成模板。     

逐步升压法制备大面积小孔径阳极氧化铝模板

在酸性电解液中,采用逐步升压法制备了高度有序的大面积阳极氧化铝（anodic aluminumoxide,AAO）模板．与传统方法制得的AAO模板相比,其有效氧化面积提高了20多倍扫描电子显微镜（scanning electron microscope,SEM）对模板微观结构的表征结果表明,二者几乎具有相同的有序度和孔密度,且孔洞分布均匀．但相比之下,采用逐步升压法制备的模板孔径要小得多,电压为42V时制得的模板的平均孔径（32．4nm）约为传统方法制得的模板平均孔径（63．2nm）的1／2．     

多孔阳极氧化铝微孔结构的调控

多孔阳极氧化铝(AAO)是一种在酸性电解液下,通过施加电压对金属铝阳极氧化获得的多孔膜材料。AAO在当今纳米材料领域有着非常多的应用,如制备纳米阵列、进行纳米复制、制备量子点等。本文采用二次氧化法制备了AAO模板,研究了硫酸、草酸两种电解液以及氧化电压对纳米孔的影响规律。采用扫描电子显微镜(SEM)对样品的表面形貌进行分析,研究了制备工艺对孔形态的影响。通过统计不同氧化电压下AAO孔的圆度和孔径的分布,发现圆度随着电压的升高而升高。孔径随电压的升高而增大,两者呈现成指数型关系。     

恒电流密度法制备大孔径高度有序阳极氧化铝模板

采用恒电流密度法,分别在草酸和磷酸的电解液中制备了阳极氧化铝模板(AAO),借助扫描电镜(SEM)观察了膜的微观形貌,结合恒电压法制备的AAO模板,研究了电解液、电流、电压等对膜的影响,并且探讨了恒电压和恒电流密度法的形成机理.结果表明:利用恒电流密度法制得的模板孔径大约在80～200nm,厚度在30～100μm,并且孔径均匀,有序性好.     

氧化铝阵列模板制备及其影响因素研究

经预处理的铝箔,分别以不同浓度硫酸和草酸为电解液,在不同阳极氧化时间、电压下,用二步阳极氧化法制备多孔有序阳极氧化铝阵列模板,用透射电镜对其形貌和结构进行了表征,用测厚仪测量了氧化膜厚度.研究结果表明,电解液种类、阳极氧化时间、电压等因素对氧化铝阵列模板外观、膜厚、孔径、孔排列有序度都有不同程度的影响.     

Highly ordered porous alumina with tailor-made pore structures fabricated by pulse anodization

A new anodization method for the preparation of nanoporous anodic aluminum oxide (AAO) with pattern-addressed pore structure was developed. The approach is based on pulse anodization of aluminum employing a series of potential waves that consist of two or more different pulses with designated periods and amplitudes, and provides unique tailoring capability of the internal pore structure of anodic alumina. Pores of the resulting AAOs exhibit a high degree of directional coherency along the pore axes without branching, and thus are suitable for fabricating novel nanowires or nanotubes, whose diameter modulation patterns are predefined by the internal pore geometry of AAO. It is found from microscopic analysis on pulse anodized AAOs that the effective electric field strength at the pore base is a key controlling parameter, governing not only the size of pores, but also the detailed geometry of the barrier oxide layer.     

用低纯度铝制备AAO模板及其结构研究

在0.3mol/dm3草酸溶液中,通过不同纯度铝的恒电位二次阳极氧化制备了纳米孔氧化铝模板,并用场发射扫描电子显微镜(FE-SEM)和原子力显微镜(AFM)观察模板结构.实验结果表明,一次氧化除膜后低纯度铝基体表面呈现较为规则的六边形结构,这种蜂巢结构有利于二次氧化过程中获得有序度更高的纳米孔模板.低纯度铝制备的模板表面被晶界分隔为微小的区域,只是在较窄区域内才出现六边形规则排列的纳米孔.恒电位40V时所得模板经扩孔处理后,孔径由35nm增大到100nm左右,且孔径大小几乎一致.从纳米孔的有序度来看,由低纯度铝制备模板还需要进一步优化阳极氧化参数.     

Synergistic effect of rare earth salt and organic acid in the anodization of aluminum in phosphoric acid

The effect of rare-earth element (cerium salt) and organic acid (citric acid) on the anodic oxide film obtained in phosphoric acid and their synergistic mechanism in the anodizing process were studied. The results show that the synergistic effect of cerium salt and citric acid in anodization of phosphoric acid can reduce surface defects, improve its microstructure and properties of the anodic oxide film. With the analysis of EDAX and XPS, the hydroxide of cerium salt was deposited on the film surface. It is deduced that cerium salt takes part in the formation of oxide film directly on the synergistic effect of citric acid.     

高度有序多孔阳极氧化铝模板的制备

为了得到纳米孔排列高度有序的多孔阳极氧化铝模板,以0.3 mol·L-1的草酸为电解液研究了模板的制备工艺.采用场发射扫描电子显微镜(FE-SEM)对多孔氧化铝模板的表面形貌进行表征,X射线衍射分析高纯铝及氧化膜的结构.实验结果表明,铝基体不经过高温退火处理,同样能够得到高度有序的氧化铝膜,简化了多孔氧化铝膜的制备工艺.分别讨论了阳极氧化电压和电解液温度对多孔阳极氧化铝膜的形貌及孔径的影响,并对一步法和两步法制得的多孔氧化铝膜进行比较,结果表明,两步阳极氧化法制备的多孔氧化铝模板的有序性优于一步氧化法.XRD分析证实,多孔氧化铝膜由非晶态的Al2O3组成.     

Fast fourier transform analysis of pore pattern in anodized alumina formed at various conditions

A quantitative investigation of the effect of process parameters such as electrolyte concentration, temperature, anodization duration and anodization potential on the pore pattern (including pore diameter and distribution) in anodic alumina was performed based on aluminum anodization experiments. Using fast Fourier transform (FFT) analysis, we developed a method to quantify the orderedness of pore distribution. We found that at a lower temperature the anodization protocol of a 1 hr first step followed by a 4 hr second step did not cause any change in pore orderedness as opposed to the anodization protocol of a 12 hr first step followed by a 1 hr second step, but at a higher temperature the former improved the pore orderedness. Increasing the electrolyte concentration, improved the pore orderedness. Varying the electrolyte concentration, temperature, and anodization duration did not have any effect on the pore diameter. Increasing the anodization potential, however, not only improved the pore orderedness but also increased the pore diameter. Linear relationships exist between the pore diameter and anodization potential and between the center to center pore spacing and applied anodization potential.     

Nanopore gradients on porous aluminum oxide generated by nonuniform anodization of aluminum

A method for surface engineering of structural gradients with nanopore topography using the self-ordering process based on electrochemical anodization of aluminum is described. A distinct anodization condition with an asymmetrically distributed electric field at the electrolyte/aluminum interface is created by nonparallel arrangement between electrodes (tilted by 45°) in an electrochemical cell. The anodic aluminum oxide (AAO) porous surfaces with ordered nanopore structures with gradual and continuous change of pore diameters from 80 to 300 nm across an area of 0.5-1 cm were fabricated by this anodization using two common electrolytes, oxalic acid (0.3 M) and phosphoric acid (0.3 M). The formation of pore gradients of AAO is explained by asymmetric and gradual distribution of the current density and temperature variation generated on the surface of Al during the anodization process. Optical and wetting gradients of prepared pore structures were confirmed by reflective interferometric spectroscopy and contact angle measurements showing the ability of this method to generate porous surfaces with multifunctional gradients (structural, optical, wetting). The study of influence of pore structures on cell growth using the culture of neuroblastoma cells reveals biological relevance of nanopore gradients and the potential to be applied as the platform for spatially controllable cell growth and cell differentiation.     

Surface morphology control on porous anodic alumina in phosphoric acid

We report the detailed surface morphology control of porous anodic aluminas (PAAs) fabricated in phosphoric acid. The surface defects can be dramatically lessened by employing the second anodization process, but there are still distortions on the surface. In the second anodizing process, the electric field distribution is not regular at the beginning due to the various pore shape and size, which leads to PAA surface distortion. One way to eliminate the surface morphology distortion is to burn the surface defects under higher temperature and higher anodizing voltage, and another way is to have well ordered nanopore array in oxalic acid before anodizing in phosphoric acid to restrict the electric field.     

Structural engineering of nanoporous anodic aluminium oxide by pulse anodization of aluminium

Nanoporous anodic aluminium oxide has traditionally been made in one of two ways: mild anodization or hard anodization. The first method produces self-ordered pore structures, but it is slow and only works for a narrow range of processing conditions; the second method, which is widely used in the aluminium industry, is faster, but it produces films with disordered pore structures. Here we report a novel approach termed "pulse anodization" that combines the advantages of the mild and hard anodization processes. By designing the pulse sequences it is possible to control both the composition and pore structure of the anodic aluminium oxide films while maintaining high throughput. We use pulse anodization to delaminate a single as-prepared anodic film into a stack of well-defined nanoporous alumina membrane sheets, and also to fabricate novel three-dimensional nanostructures.     

Study of nanopores ordering in anodic aluminum oxide templates achieved by three step process

Enhancement of naturally-occurred self ordering nanopores in anodic aluminum oxide membrane by performing three-step anodic oxidation process has been reported. Naturally-occurred self ordering of nanopores in anodic aluminum oxide membrane has brought it into the applications of template for fabrication of nanoscale materials. Three-step anodic oxidation method was used to achieve self-ordering of nanopores. Effect of duration of first and second steps on the ordering of nanopores was investigated. The current-time curves recorded during anodization elucidate an almost same behavior for all three steps. Scanning electron micrographs show hexagonally arranged 45 nm pores in a manner which contribute into the formation of highly ordered areas, called domains. Larger ones are clearly observed over the surface, for samples with longer first and second anodization steps.     

Effects of the hydrogen content on the development of anodic aluminum oxide film on pure aluminum

In this study, high purity aluminum (Al) samples containing different levels of hydrogen were used as a base metal for anodization. To ensure constant current densities during the experiments, the voltage-time (V-t) curves were recorded. The differential ΔV/Δt curves were plotted and the energy consumed during different steps of anodization was calculated. Experimental observations show that differences in the hydrogen content affected the amount of energy consumed. The process was divided into three steps.When the voltage response at the end of step 2 exceeded 25 V, the energy consumed in steps 2 + 3 reached or exceeded 7.4 J/cm², and the pore channels branched or merged, creating a spike in the ΔV/Δt curves in step 3. A combination of the effects of the high voltage response at the end of step 2 and the high hydrogen content in the Al samples led to the formation of an anodic aluminum oxide (AAO) film in the sulfuric acid solution, which produced crystallized boehmite. This study proposes a unique tool for understanding certain special anodic behaviors of pure Al, wherein the branching or merging of pore channels and the partial crystallization of the AAO film can be ascertained by looking at the irregularities in the ΔV/Δt curves obtained in step 3.