Porous Alumina Films Research Articles

On the Occurrence of Domain Boundaries and Defects in Self-Organized Ordered Porous Anodic Alumina Systems.

The formation of domains and defects is a part of every self-organized structure without prepatterning which evolves from the electrochemical oxidation of valve metals like Ti, Al or Ta. Defects and domains, especially in highly ordered porous alumina films (PAOX), are one of the most studied phenomena in the current literature. The focus is on understanding their formation in order to find parameters to minimize their amount for applications that require the most highly organized structures. In this letter we give a solution to this problem by showing that the occurrence of defects and domains is an unavoidable consequence of the underlying self-organized process due to the simultaneous impact of the minimum (MINEP) and maximum (MAXEP) entropy production principle. As a consequence, experimental procedures to manufacture defect-free PAOX-films from a self-organization process face a fundamental limitation.

High-Performance Humidity Sensor Capable for Monitoring Low-Moisture Levels in Energy Industries

Humidity sensors are extensively used in industrial processing and environmental control. There are two categories of humidity sensors: High-humidity (relative humidity) measurement and Low-humidity (moisture) measurement. The proper units for low-humidity measurement are dew point and parts per million in volume (ppmv) or parts per billion in volume (ppbv). It is very important to monitor moisture levels in natural gas during processing and transportation in pipelines. It is of critical importance to monitor moisture levels in lithium-ion battery manufacturing. In these cases, the moisture levels are limited to be less than -50°C dew point or 40 ppmv. The conventional relative humidity sensors cannot be used because of their low sensitivity. The dew point sensors on the market are polymer-based and gamma-phase-alumina based. The polymer-based sensors have low sensitivity, which can only accurately detect moisture levels of -60°C dew point and higher. The gamma-phase alumina sensors suffer from long-term drift due to phase change.We present novel high-performance humidity sensors based on porous alpha-phase alumina and silicon dioxide nanostructures, which are capable of detecting moisture levels as low as -100°C dew point or 13 ppbv with excellent long-term stability. The porous alpha-phase alumina films were produced by anodic-spark-deposition on aluminum substrates in which electric sparks were produced due to high-voltage anodization (>120V). Local high-temperature (about 2200°C) at the points of sparks converted the amorphous alumina into alpha-phase alumina (Sapphire). It provides an extremely stable structure for humidity sensors. Hydrophilic silicon dioxide films deposited by atomic layer deposition was used as sensing materials. The sensors’ sensitivity, temperature coefficient, response speed, and long-term stability were studied in details. The sensors have great promise for monitoring moisture levels in natural gas industry and lithium-ion battery manufacturing.

The effect of the degree of hydration of aluminium oxide thin films on the afterglow luminescence phenomena

The occurrence of afterglow luminescence in aluminum oxide thin films obtained by non-electrolytic aluminum oxide conversion coating has been proved. The kinetic parameters of luminescence decay and its spectral distribution were determined using the single photon counting method. The obtained samples of hydrated aluminum oxide, supported on metallic aluminum, were subjected to dehydration and dehydroxylation. The process of dehydroxylation led to a significant (by over two orders of magnitude) increase in the efficiency of afterglow luminescence. On the basis of the luminescence decay spectrum, the emitters in the systems studied were identified to be oxygen vacancies in the structure of Al2O3, including F, F2, F+. Moreover, a high probability of involvement of electrons from the conductivity band and F and F+ states photoconversion in determination of the character of afterglow luminescence was indicated. Durations of afterglow luminescence measured for the barrier layers and porous aluminum oxide films, obtained by electrochemical oxidation, were compared. Significant differences were detected between the kinetic parameters of luminescence decay and the character of emission spectra, whose analysis permitted proposing mechanisms of the processes.

Enhanced bonding of polyphenylene sulfide-aluminum alloy composites using combined mild and hard anodizing techniques

High-strength direct joining between polymers and Al has attracted considerable attention, particularly for reducing the weight device. In this study, porous anodic alumina (PAA) films were fabricated on a commercial 6063 Al alloy using with mild and hard anodizing with varying durations, followed by etching. Subsequently, polyphenylene sulfide (PPS) was directly joined with Al through injection molding. The correlations between the interface bond strength of PPS-Al joints and the Al oxidation duration were systematically investigated. The porosity, diameter of nanopore, and wettability of anodic aluminum oxide (AAO) film surface significantly influenced the bonding strength of PPS-Al composite structure. The porosity increased with an etching duration, increasing the bonding strength. However, excessive porosity (>54 %) weaken the films and reduced their bonding strengths. When the durations of mild anodizing (MA), hard anodizing (HA), and etching treatment were set to 30, 30, and 60 min, respectively, the maximum bonding strength reached 25.2 MPa, approximately 77 % of the base-material shear strength. Scanning electron microscopy revealed nanopillars with two different top sizes (approximately 80 and 110–130 nm) on the surface of injection-molded PPS, which were attributed to the different anodizing preparation voltage. These findings are generally significant for the realization for high-strength direct-bonded polymer-Al joints.

A multi-strategy coating for Al alloy based on orientationally arranged nanosheets doped SiO2 coating and corrosion inhibitor loaded porous anodic alumina film

Although aluminum alloys are widely used in various industries, their wear and corrosion resistance are still needed to be enhanced. In this study, a robust anti-corrosion composite coating was prepared on the surface of Al alloy based on multiple reinforcement strategies. The composite coating is consisted of horizontally arranged and functionally modified h-BN nanosheets doped SiO2 coating (SiO2-hBN(NH3+) coating) and corrosion inhibitor MBT loaded porous anodic alumina (PAA-MBT) film. Results show that the composite coating prepared in this work has excellent corrosion resistance due to the effect of the extended penetration path of corrosive medium by h-BN(NH3+) nanosheets, the full-thickness hydrophobicity of the SiO2 coating, the corrosion inhibition of the MBT released from the PAA film and the physical barrier of the entire coating system. In addition, the composite coating also exhibits good mechanical properties including high hardness, high bonding strength and superior wear resistance. This work provides a novel design of protective coating with excellent anti-corrosion resistance and mechanical properties, which has a promising prospect in the development of superior long-term anti-corrosion coatings for aluminum alloy.

Effect of Oxalic Acid Additives on Aluminum Anodizing in Formic Acid Containing Ammonium Heptamolybdate

This paper reports a systematic study of the role of oxalic acid additives in aluminum anodizing in formic acid containing ammonium heptamolybdate. Adding oxalic acid in a concentration range of 5–20 mM to the 0.4 M formic acid solution containing 0.03 M ammonium heptamolybdate improves anodic film growth, increasing the film thickness and smoothing strongly wavy interface between the film and aluminum, and adding 100 mM of oxalic acid results in an almost complete block of the regular anodic film formation. In the case of aluminum anodizing in formic acid, the ammonium heptamolybdate additive prevents aluminum dissolution more effectively than only oxalic acid. The role of oxalic acid in this process is only to improve film growth and morphology. However, ammonium heptamolybdate improves film growth by increasing its thickness. Linear sweep voltammetry studies combined with SEM investigations of alumina growth show that in heptamolybdate-containing electrolytes, a thin porous alumina film is formed at the beginning of the process. Then, when the electrolyte oxidation potential is reached, the thin film on the surface breaks, resulting in a significant increase in the anodizing surface, and anodic oxide begins to grow rapidly.

Wearable electret based metal oxide nanostructure for self-powered respiration monitoring

Exhaled human breath contains information regarding metabolic and physiological data, and its monitoring can play a crucial role in the early clinical diagnosis and treatment of diseases. An energy-autonomous breath monitoring device was designed by anodizing Al sheet (Nose Bridge), present in existing commercial, medical, and industrial masks for monitoring breath. The electrochemically grown porous anodic alumina (PAA) film acts as the electret layer for generating and trapping charge carriers and has the dual function of energy harvesting and sensing. The device is based on the principle of a triboelectric nanogenerator (TENG), where PAA and Polydimethylsiloxane (PDMS) were used as tribo-electrodes, generating a peak-to-peak voltage of 225 V and a short circuit current of 1 μA with a power density of 110.75 mW/m2. PAA with small pore diameter, depth, and long-range ordering exhibit the best performance. The nanoporous structure of PAA provides an exceptionally high surface area of 14.31 m2/g, significantly enhancing the performance. The device exhibits an exceptionally high sensitivity of −15.84/RH% in the 25–90 RH% detection range, with a hysteresis of 2.2% at 65 RH%. This research paves the way for developing personalized healthcare monitoring systems by integrating anodized nose bridges in medical and industrial masks that provide mechanical support and can be used for energy harvesting and breath monitoring.

Effect of Al Polishing Conditions on the Growth and Morphology of Porous Anodic Alumina Films.

The conditions applied during the electrochemical polishing of aluminum were found to be important parameters for the successive formation of nanoporous alumina films. First, a high-purity Al foil was electrochemically polished in an aqueous solution containing C2H5OH and HClO4 at various sets of conditions, such as applied potential (5-35 V), temperature (0-20 °C), and process duration (10-180 s). Extensive studies of the topography of Al after polishing by scanning electron microscopy and atomic force microscopy allow verification of the correlations between conditions applied during the substrate pretreatment and dimensions of the nanopatterns generated on the metal surface. Next, Al polished samples at two different sets of conditions were used as starting materials for anodization. Unpolished Al samples were also anodized for reference. It was confirmed that electropolishing conditions do not significantly affect the oxide growth rate during anodization and the efficiency of anodic film formation. On the contrary, it was proved that the dimensions of the surface texture formed during Al polishing significantly affect the morphology and pore order within the anodic film. Therefore, it can be stated that it is possible to tune to some extent the arrangement of nanochannels within anodic aluminum oxide films by simply changing conditions during the electropolishing procedure..

Optical Fiber Temperature and Humidity Dual Parameter Sensing Based on Fiber Bragg Gratings and Porous Film.

A porous anodic alumina film is proposed to construct an optical fiber temperature and humidity sensor. In the sensor structure, a fiber Bragg grating is used to detect the environment temperature, and the porous film is used to detect the environment humidity. The proposed porous anodic alumina film was fabricated by anodic oxidation reaction, and it is suitable for the use of humidity detection due to its porous structure. Experimental results show the temperature sensitivity of the proposed sensor was 10.4 pm/°C and the humidity sensitivity of the proposed sensor was 185 pm/%RH.

High-Efficiency Metal-Insulator-Metal Electron Emitter Based on Porous Alumina Film

High-Efficiency Metal-Insulator-Metal Electron Emitter Based on Porous Alumina Film

Se-doped Nb2O5–Al2O3 composite-ceramic nanoarrays via the anodizing of Al/Nb bilayer in selenic acid

Novel arrays of Nb2O5-based ceramic nanostructures of various sizes (9–210 nm) and morphologies (dots, goblets, rods) aligned on substrates are fabricated via the anodizing of a thin Nb film through the initially formed porous anodic alumina (PAA) film in 1.5 M selenic acid (H2SeO4) – a new aqueous electrolyte generating extraordinarily thinner PAA pores than any other solutions. Accordingly, the nanostructures formed in the selenic acid are 1.3-fold thinner and better self-ordered than their counterparts formed from the same Al/Nb precursor bilayer in a reference oxalic-acid electrolyte. The nanostructures have a dual (core/shell) composition: the inner material (the core) is stoichiometric Nb2O5, whereas the outer layer (the shell) is a few nm-thick substoichiometric NbOx mixed with Al2O3. The composite-ceramic nanoarrays grow doped with selenium species such as selenate (SeO42−) and selenide (Se2−) anions originating from the electrolyte and migrating inward under the high electric field. The incorporated Se species do not contribute to photoluminescence emission nor hinder the Raman signal from the nanoarrays, which makes them highly promising as Nb2O5-based SERS biosensing substrates. The planar PAA-inbuilt Se-doped Nb2O5–Al2O3 nanostructured ceramic film performs like a high-k low-loss low-leakage-current dielectric promising for on-chip integration. More potential applications of the Se-doped ceramic nanoarrays developed here include biomedical antibacterial coatings, advanced superhydrophobic surfaces, gas-sensing, and catalytic layers.

Understanding the fast formation mechanism of hard nanoporous alumina films on aluminum in acidic solutions containing nitric acid

Nanoporous alumina films formed on aluminum via anodization are widely used for scientific and technical purposes owing to their various advantageous properties, including excellent corrosion and wear resistance, good thermal and electrical insulation, and facile producibility at low cost. Herein, we report a novel approach to fabricate hard porous anodic alumina (PAA) films by adding an appropriate amount of nitric acid to sulfuric-, oxalic-, and phosphoric-acid solutions at critical high current densities. The effects of the nitric additives on the anodizing behavior, film growth mechanism, microstructure, chemical composition, film thickness, microhardness, and appearance of the PAA films formed from various solutions were systematically investigated. The addition of nitric acid enhanced the formation of alumina and resulted in fast growth rates of 196 μm/h and 166 μm/h for sulfuric- and oxalic-based solutions, respectively, while maintaining high hardness of approximately 380 and 430 HV0.1, respectively. The surface hardness of the films decreased to some extent with the increase in nitric acid concentration and/or film thickness owing to the strong corrosive nature of nitric acid during prolonged anodization, although nitrogen inclusion in anodic alumina films was not detected through X-ray photo-electron spectroscopy, which differs from the other acidic anions. In particular, the barrier layer thickness and pore intervals of PAA films increased with the nitric concentration in the aforementioned solutions, leading to a fast growth rate and high hardness inside the films.

A Novel Polishing Process for Ultra-Smooth Aluminum Surfaces via Anodizing in Sodium Metaborate

A novel ultra-smoothing process for aluminum surfaces was developed using porous alumina formation and subsequent oxide dissolution. A submicron-scale periodic dimpled aluminum surface with an arithmetic mean roughness of 31.5 nm was prepared by anodizing in an etidronic acid solution. This dimpled aluminum specimen was then anodized in a sodium metaborate (NaBO2) solution to form a unique porous alumina film with an extremely flat barrier layer, which differs from the typical hemispherical barrier layer. The outer porous layer became thicker with time during anodizing, whereas the thickness and smoothness of the inner barrier layer were maintained without oxide breakdown. As the porous alumina film was chemically removed in a CrO3/H3PO4 solution, a smooth aluminum surface was exposed. The mean roughness of the aluminum surface drastically decreased to 0.5 nm by short-term anodizing for 15 min and slightly decreased with further anodizing. As a result, an ultra-smooth aluminum surface measuring 0.4 nm in roughness, which is much smaller than that of an electropolished aluminum surface (1.3 nm), was successfully obtained via anodizing in NaBO2 and subsequent oxide dissolution. Our smoothing process was compared with conventional smoothing processes such as electropolishing and barrier oxide formation.

Dielectric and thermal properties of rubidium nitrate embedded into porous aluminum oxide films

The results of studying the dielectric permittivity, the third harmonic coefficient, and the DTA signal for Al2O3 nanoporous matrices filled with rubidium nitrate are presented. A shift of the phase transition T c ≈ 437 K by 3 K to the low-temperature region and an increase in the temperature hysteresis of the phase transition from 14 K for polycrystalline RbNO3 to 33 K for RbNO3 in the pores of the Al2O3 oxide film were found.

Electrochemical Impedance Spectroscopy Study of Porous Anodic Alumina Films Fabricated at Low Temperature

A method of fabrication of AAO film in 0.3 mol/L H2C2O4 by adding 1,2-propanediol(PROH) and at sub-zero temperature has been proposed. The electrochemical characteristics of the barrier and porous layers of AAO films before and after pore-filling are examined using electrochemical impedance spectroscopy (EIS). It is shown that the high and medium frequency range corresponds to the barrier layer properties and the low frequency ranges reflect the sealed porous layer properties. The calculated thickness of the barrier layer is in the range of 1 ~ 18 nm. The resistance (Rb) and the thickness (δb) of the barrier layer increase and the capacitance of the barrier layer (CPEb) decrease with the volume percentage of PROH increasing from in electrolyte from 25 % to 75 %. The surface non-homogeneity of AAO film goes better by pore-filling, leading to a decrease in the capacitance of the porous layer (CPEp) and an increase in the porous layer thickness.

Effects of anion incorporation on the local structure of porous-type amorphous alumina prepared by anodization: NMR study of Al coordination numbers

Although anodization is an essential technology that has supported the aluminum industry for nearly a century, the atomistic structure of the formed alumina films has not completely understood. Here we used NMR spectroscopy to clarify the factors affecting local structure of anodic porous alumina films prepared under various electrolytic conditions. For anion-free amorphous alumina films prepared using chromic acid, the local structure does not depend on electrolytic factors. For films prepared using phosphoric acid, the average coordination number was lower than that of anion-free alumina. On the other hand, films prepared using oxalic and sulfuric acids showed the average coordination numbers higher than that of anion-free alumina. We reveal that aluminum coordination number of anodic porous alumina are affected by anion species and anion content. In addition, the depth of anion incorporation into cell walls, or compositional uniformity, is quite important for accurate interpretation of NMR spectra.

A Novel Sensor for Fruit Ripeness Estimation Using Lithography Free Approach

A flexible tactile sensor has the ability to sense and characterize the firmness and mechanical stiffness of the object. In this work, we demonstrate a low-cost, highly sensitive, flexible capacitive tactile sensor using a nanoneedle-patterned polydimethylsiloxane (PDMS) as a dielectric layer to detect the ripeness of the fruits. The nanoneedle-patterned PDMS was formed using an anodic oxidized porous alumina film as a mold. The developed tactile sensor exhibited high sensitivity due to the high deformity and elasticity of the nanoneedles on the PDMS layer. The higher sensitivity of 1.042–0.67 kPa−1 for a low-pressure regime below 0.2 kPa and the lower sensitivity of 0.35 kPa−1 for a pressure range above 0.6 kPa were demonstrated. This corresponds to a ~12% change in capacitance at 0.1-kPa pressure. Loading unloading tests for over 500 cycles were performed to confirm the absence of hysteresis. The mechanical elastic modulus of different tomato samples was tested using the tactile sensor and a universal test machine. The device could easily discriminate tomatoes of different stiffness. The tomato ripeness detection experiments demonstrate that the sensor can be used in robotic sensors, to estimate the qualitative ripeness of the fruits, during harvesting and transportation. This concept can be utilized in assessing ripeness levels of fruits like mangoes, kiwis, pears, avocados, sapodilla, and so on, after adequate recalibration of the sensor, leading to different sensing ranges.

Ingenious Fabrication of Ag-Filled Porous Anodic Alumina Films as Powerful SERS Substrates for Efficient Detection of Biological and Organic Molecules.

Surface-enhanced Raman scattering (SERS) has been widely used to effectively detect various biological and organic molecules. This detection method needs analytes adsorbed onto a specific metal nanostructure, e.g., Ag-nanoparticles. A substrate containing such a structure (called SERS substrate) is user-friendly for people implementing the adsorption and subsequent SERS detection. Here, we report on powerful SERS substrates based on efficient fabrication of Ag-filled anodic aluminum oxide (AAO) films. The films contain many nanopores with small as-grown inter-pore gap of 15 nm. The substrates are created by electrochemically depositing silver into nanopores without an additional pore widening process, which is usually needed for conventional two-step AAO fabrication. The created substrates contain well-separated Ag-nanoparticles with quite a small inter-particle gap and a high number density (2.5 × 1010 cm−2). We use one-step anodization together with omitting additional pore widening to improve the throughput of substrate fabrication. Such substrates provide a low concentration detection limit of 10−11 M and high SERS enhancement factor of 1 × 106 for rhodamine 6G (R6G). The effective detection of biological and organic molecules by the substrate is demonstrated with analytes of adenine, glucose, R6G, eosin Y, and methylene blue. These results allow us to take one step further toward the successful commercialization of AAO-based SERS substrates.

The effect of dissolution by periodic reverse current on the microstructure of bamboo-shaped porous anodic alumina

• Periodic reverse current with small amplitude can promote the growth of the porous layer. • Periodic reverse current has the effect of pore expansion. • The water reduction speed increases during the reverse voltage stage. • The ions driven by the electric field change with the direction of current. • H+ (H2O) and OH− are the main ions that move in the reverse voltage stage. In this paper, the effects of a cyclic anodizing method with the introduction of periodic reverse current are reported. The effects of the periodic reverse current on the microstructure of bamboo-shaped porous anodic alumina (PAA) film are investigated using positive and negative current triangular waveforms. The results of the experiment showed that when the reverse current in each current cycle was I D ' = -5 mA, the growth velocity was the fastest. The analysis found that the introduction of the periodic reverse current was beneficial to increasing the growth velocity of the porous anodic alumina film and had the additional effect of pore expansion. However, with any further increase of the periodic reverse current, the growth velocity of the porous anodic alumina film gradually decreased, and the period length showed a decreasing trend. The main reason for this phenomenon is that in a larger reverse voltage phase, the ions driven by the electric field are mainly H + (H 2 O) and OH − . Then the reaction that occurs is mainly dissolution. With large pore size and adjustable period length, this porous anodic alumina film can be used as a template for the synthesis of nanomaterials, which have practical significance for the synthesis of nanodevices.

Pulsed Plasma Electrolytic Oxidation as Strategy to Produce Optical Selective Surfaces

Porous alumina (PA) films have been investigated for selective optical surface application. In this work, we use pulsed plasma electrolytic oxidation (PPEO) to produce porous surfaces in aluminum. During the PPEO processing, image of plasma on the samples and active species present in micro-discharges were documented using CCD camera and standard optical emission spectroscopy (OES) technique. Porosity was controlled by varying the pulsewidth ( <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$T_{\mathrm {on}}$ </tex-math></inline-formula> ) and treatment time, keeping the pulse repetition time ( <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$T_{\mathrm {off}}$ </tex-math></inline-formula> ) constant. The optical reflectance and thermal efficiency of the samples were investigated for samples with different microstructure, crystalline phase and chemical composition. It is shown that coatings produced by shorter pulses ( <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$T_{\mathrm {on}}$ </tex-math></inline-formula> ) with smaller time of treatment resulted in smallest pore size and more uniform distribution. These results positively influenced the reflectance and thermal efficiency of the surfaces.