Experimental validation of the novel theory explaining self-organization in porous anodic alumina films

Applied Surface Science

Nakajima

Kawashima

et al. 2014

The growth behavior of anodic porous alumina formed by anodizing in novel electrolyte solutions, the cyclic oxocarbon acids croconic and rhodizonic acid, was investigated for the first time. High-purity aluminum specimens were anodized in 0.1 M croconic and rhodizonic acid solutions at various constant current densities. An anodic porous alumina film with a cell size of 200-450 nm grew uniformly on an aluminum substrate by rhodizonic acid anodizing at 5-40 Am -2 , and a black, burned oxide was formed at higher current density. The cell size of the porous alumina increased with current density and corresponding anodizing voltage. Anodizing in croconic acid at 293 K caused the formation of thin anodic porous alumina films as well as black, thick burned oxides. The uniformity of the porous alumina improved by increasing the temperature of the croconic acid solution, and anodic porous alumina films with a uniform film thickness were successfully obtained. Our experimental results showed that the cyclic oxocarbon acids croconic and rhodizonic acid could be employed as a suitable electrolyte for the formation of anodic porous alumina films.Key words: Aluminum; Anodizing; Anodic Porous Alumina; Croconic Acid; Rhodizonic Acid IntroductionThe anodizing of aluminum in several different acidic solutions causes the formation of anodic porous alumina (i.e., porous anodic oxide film) with characteristic nanofeatures on aluminum substrates. Porous alumina consists of nano-scale hexagonal cells perpendicular to the substrate, and each cell possesses a nanopore at its center [1,2]. These cells are self-ordered by anodizing under appropriate electrochemical conditions, especially under a high electric field [3,4]. When anodic porous alumina is immersed in boiling distilled water after anodizing, the nanopores are filled by hydroxide (pore-sealing) [5,6]. The sealing process causes the formation of a highly crystalline hydroxide layer on the surface of the anodic oxide, and the hydroxide layer is highly dissolution-resistant in acidic and alkaline solutions. Using these characteristic structural and chemical properties, anodic porous alumina has been widely investigated for many applications: antireflection structures [7,8] [50] acid have been reported to date for the fabrication of anodic porous alumina. Oxalic and malonic acid anodizing have been reported to give rise to self-ordering behavior under suitable anodizing conditions. The organic and inorganic electrolytes used to fabricate anodic porous alumina possess low dissociation constant (pKa) in aqueous solution, except for glycolic and formic acid, are diacids or triacids. However, glycolic and formic acid form dimers via hydrogen bonding in aqueous solution and may behave like diacids [52,53]. The nanofeatures of anodic porous alumina, including cell size (i.e., interpore distance) and pore diameter, are limited by these electrolytes during anodizing. Therefore, the discovery of additional electrolytes is very important in expanding the applicability of porous alum...

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

Fabrication of anodic porous alumina via anodizing in cyclic oxocarbon acids

Applied Surface Science

Nakajima

Kawashima

et al. 2014

“…However, malonic and tartaric acids have seldom been used for nanostructure fabrication because they do not perform as well with regards to self-ordering as the three major electrolytes. Chromic (H 2 CrO 4 ) [41][42][43], formic (HCOOH) [44], malic (HOOC-CH(OH)-CH 2 -COOH) [27,45,46], citric (HOOC-CH 2 -C(OH)(COOH)-CH 2 -COOH) [27,47,48], glycolic (CH 2 OH-COOH) [27], squaric (3,4-dihydroxy-3-cyclobutene-1,2-dione) [49], tartronic (HOOC-CH(OH)-COOH) [50], and acetylenedicarboxylic (HOOC-C≡C-COOH) [51] acids have also been reported as electrolytes used to fabricate porous alumina that has characteristic nanostructure morphologies.…”

Section: Introductionmentioning

confidence: 99%

“…Anodic porous alumina is typically fabricated on an aluminum substrate using electrochemical anodizing (or anodization) [22][23][24][25][26]. In several acidic electrolyte solutions, the porous alumina fabricated by anodizing is self-ordered when prepared at the appropriate electrochemical conditions, including appropriate concentrations, temperatures, and voltages (or electrochemical potentials) [27][28][29][30] [50], and acetylenedicarboxylic (HOOC-C≡C-COOH) [51] acids have also been reported as electrolytes used to fabricate porous alumina that has characteristic nanostructure morphologies.In addition to these acidic electrolytes, alkaline and neutral solutions used for porous alumina fabrication were reported by several research groups. Takahashi et al reported that a porous anodic oxide film could be formed by anodizing in an H 3 BO 3 /Na 2 B 4 O 7 neutral borate solution at a high temperature [52].…”

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confidence: 99%

Self-Ordering Behavior of Anodic Porous Alumina via Selenic Acid Anodizing

Nishinaga

Natsui

et al. 2014

Electrochimica Acta

The self-ordering behavior of anodic porous alumina that was formed by anodizing in selenic acid electrolyte (H 2 SeO 4 ) at various concentrations and voltages was investigated with SEM and AFM imaging. A high purity aluminum foil was anodized in 0.1-3.0 M selenic acid solutions at 273 K and at constant cell voltages in the range of 37 to 51 V. The regularity of the cell arrangement increased with increasing anodizing voltage and selenic acid concentration under conditions of steady oxide growth without burning. Anodizing at 42-46 V in 3.0 M selenic acid produced highly ordered porous alumina. By selective dissolution of the anodic porous alumina, highly ordered convex nanostructures of aluminum with diameters of 20 nm and heights of 40 nm were exposed at the apexes of each hexagonal dimple array. Highly ordered anodic porous alumina with a cell size of 102 nm from top to bottom can be fabricated by a two-step selenic acid anodizing process, that includes the first anodizing step, the selective oxide dissolution, and the second anodizing step.Key words: Aluminum; Anodizing; Anodic Porous Alumina; Selenic Acid IntroductionBarrier anodic oxide films and porous anodic oxide films on aluminum have been widely investigated by many researchers in the fields of surface finishing [1][2][3], electrolytic capacitor application [4][5][6], and micro-and nano-structure fabrication [7][8][9]. Recently, highly ordered anodic porous alumina with a cell size on the scale of 10-100 nm has been studied for potential use in various ordered-nanostructure applications [10][11][12][13][14][15][16][17][18][19][20][21]. Anodic porous alumina is typically fabricated on an aluminum substrate using electrochemical anodizing (or anodization) [22][23][24][25][26]. In several acidic electrolyte solutions, the porous alumina fabricated by anodizing is self-ordered when prepared at the appropriate electrochemical conditions, including appropriate concentrations, temperatures, and voltages (or electrochemical potentials) [27][28][29][30] [50], and acetylenedicarboxylic (HOOC-C≡C-COOH) [51] acids have also been reported as electrolytes used to fabricate porous alumina that has characteristic nanostructure morphologies.In addition to these acidic electrolytes, alkaline and neutral solutions used for porous alumina fabrication were reported by several research groups. Takahashi et al. reported that a porous anodic oxide film could be formed by anodizing in an H 3 BO 3 /Na 2 B 4 O 7 neutral borate solution at a high temperature [52]. Baron-Wiechec et al. investigated aluminum anodizing in a borax (Na 2 B 4 O 7 ) solution at 333 K and successfully obtained porous alumina [53]. Noguchi et al. investigated the anodizing behavior of aluminum in propylenediamine and choline alkaline solutions containing ammonium fluoride, ammonium tartrate, ammonium carbonate, and ammonium tetraborate, and obtained anodic porous alumina with nanopores that were 10-150 nm in diameter [54]. However, it is difficult to form a highly ordered porous alumina by anodiz...

“…Cyclic oxocarbonic acids such as squaric [24], croconic, and rhodizonic [25] acid were very recently determined to be suitable organic electrolytes for fabricating porous alumina, although the details of the growth behavior are still unknown. Carboxylic acids can also be employed as suitable electrolytes for fabricating porous alumina, including oxalic [26,27], malonic [28,29], citric [30,31], malic [32], acetylenedicarboxylic [33], tartaric [34,35], tartronic [36], glycolic [37], and formic [38] acid. Because the nanostructural features and chemical properties of anodic porous alumina are determined and limited by the electrolyte used [39], the discovery of a new suitable electrolyte would expand the applicability of porous alumina.…”

Section: Introductionmentioning

confidence: 99%

Growth behavior of anodic oxide formed by aluminum anodizing in glutaric and its derivative acid electrolytes

Nakajima

Applied Surface Science

Natsui

2014

The growth behavior of anodic oxide films formed via anodizing in glutaric and its derivative acid solutions was investigated based on the acid dissociation constants of electrolytes. High-purity aluminum foils were anodized in glutaric, ketoglutaric, and acetonedicarboxylic acid solutions under various electrochemical conditions. A thin barrier anodic oxide film grew uniformly on the aluminum substrate by glutaric acid anodizing, and further anodizing caused the film to breakdown due to a high electric field. In contrast, an anodic porous alumina film with a submicrometer-scale cell diameter was successfully formed by ketoglutaric acid anodizing at 293 K. However, the increase and decrease in the temperature of the ketoglutaric acid resulted in non-uniform oxide growth and localized pitting corrosion of the aluminum substrate. An anodic porous alumina film could also be fabricated by acetonedicarboxylic acid anodizing due to the relatively low dissociation constants associated with the acid. Acid dissociation constants are an important factor for the fabrication of anodic porous alumina films.Keywords: Aluminum; Anodizing; Glutaric Acid; Ketoglutaric Acid; Acetonedicarboxylic Acid IntroductionAnodic porous alumina with numerous vertical, nano-scale pores can easily be fabricated via aluminum anodizing in several types of acidic aqueous solutions and has been widely applied in the fields of corrosion protection and electronic applications [1][2][3][4][5][6]. In particular, the development of highly ordered anodic porous alumina, which is fabricated via self-ordering and two-step anodizing under appropriate electrochemical conditions, has expanded the applicability of porous alumina [7]. Accordingly, plasmonic devices [8], antireflection polymer structures[9], optical devices [10], and high-density recording media [11] have been successfully fabricated through the combination of methods for developing highly ordered anodic porous alumina and other nanostructure fabrication techniques.The electrolyte species used for anodic porous alumina fabrication can be specifically classified into the following three groups: inorganic, organic cyclic oxocarbonic, and organic carboxylic acids. It is a well-known experimental fact that anodic porous alumina can be formed by anodizing in these acidic electrolytes, which provide low acid dissociation constants. To date, sulfuric [12][13][14][15][16], selenic [17,18], phosphoric [19,20], and chromic[21] acids have been reported as useful inorganic electrolytes for fabricating anodic porous alumina. The ideal cell arrangement of porous alumina can be achieved via sulfuric, selenic, and phosphoric acid anodizing, whereas poorly ordered porous alumina is fabricated via chromic acid anodizing [22,23]. Cyclic oxocarbonic acids such as squaric [24], croconic, and rhodizonic[25] acid were very recently determined to be suitable organic electrolytes for fabricating porous alumina, although the details of the growth behavior are still unknown. Carboxylic acids can also be employed ...