A tracer investigation of chromic acid anodizing of aluminium

Garcia-Vergara, S.J.; Skeldon, P.; Thompson, G.E.; Habazaki, H.

doi:10.1002/sia.2601

Cited by 65 publications

(51 citation statements)

References 35 publications

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“…Malonic acid (HOOC-CH 2 -COOH) and tartaric acid (HOOC-(CHOH) 2 -COOH), typical dicarboxylic acids, have also been reported to support the fabrication of highly ordered porous alumina fabrication at 120 V and 195 V, respectively [30,31]. In addition, several other electrolytes, such as chromic (H 2 CrO 4 ) [32,33], malic (HOOC-CH(OH)-CH 2 -COOH) [23,34], citric (HOCO-CH 2 -C(OH)(COOH)-COOH)) [23], and glycolic (CH 2 OH-COOH) [23] acids, have been reported as anodizing electrolytes to date. However, the formation of thick porous alumina with straight nanopores by anodizing in chromic acid is difficult because of branching and colony-forming nanopores [35].…”

Section: Introductionmentioning

confidence: 99%

Fabrication of Anodic Porous Alumina by Squaric Acid Anodizing

Kikuchi¹,

Yamamoto²,

Natsui³

et al. 2014

Electrochimica Acta

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The growth behavior of anodic porous alumina formed via anodizing in a new electrolyte, squaric acid (3,4-dihydroxy-3-cyclobutene-1,2-dione), is reported for the first time. A high-purity aluminum foil was anodized in a 0.1 M squaric acid solution at 293 K and a constant applied potential of 100-150 V. Anodic oxides grew on the aluminum foil at applied potentials of 100-120 V, but a burned oxide film was formed at higher voltage. Anodic porous alumina with a cell size of approximately 200-400 nm and sub-100-nm-scale pore diameter was successfully fabricated by anodizing in squaric acid. The cell size of the anodic oxide increased with anodizing time because of the uneven growth of the porous layer. The anodic porous alumina obtained by squaric acid anodizing consists of amorphous Al 2 O 3 containing 5-6 at% carbon from the electrolyte. Fig. 1). The morphology of anodic porous alumina, especially its cell size (identical meaning to interpore distance) and pore diameter in the porous layer, is limited by the electrolyte and voltage (electrochemical potential) applied during anodizing [23,24]. Fig. 1 summarizes the anodizing electrolytes that have been reported to date for porous alumina fabrication. Sulfuric (H 2 SO 4 ), oxalic ((COOH) 2 ), and phosphoric (H 3 PO 4 ) acids are well-known, self-ordering anodizing solutions for porous alumina fabrication, and highly ordered porous alumina can be obtained by anodizing in these solutions at constant voltages of 18-25 V, 40 V, and 160-195 V, respectively [24-29]. Malonic acid (HOOC-CH 2 -COOH) and tartaric acid (HOOC-(CHOH) 2 -COOH), typical dicarboxylic acids, have also been reported to support the fabrication of highly ordered porous alumina fabrication at 120 V and 195 V, respectively [30,31]. In addition, several other electrolytes, such as chromic (H 2 CrO 4 ) [32,33], malic (HOOC-CH(OH)-CH 2 -COOH) [23,34], citric (HOCO-CH 2 -C(OH)(COOH)-COOH)) [23], and glycolic (CH 2 OH-COOH) [23] acids, have been reported as anodizing electrolytes to date. However, the formation of thick porous alumina with straight nanopores by anodizing in chromic acid is difficult because of branching and colony-forming nanopores [35]. Although citric acid anodizing has already been used for nanostructure fabrication [36], other organic electrolytes, including malic and glycolic acid solutions, cause the formation of non-uniform anodic porous alumina [23,34]. Therefore, five self-ordering electrolytes, namely, sulfuric, oxalic, and phosphoric acids, are generally selected for anodic porous alumina fabrication by many researchers.In recent years, new anodizing procedures using an effective experimental approach and optimal anodizing conditions have been reported by several researchers to control the nano-scale features of anodic porous alumina. Lee et al. studied the rapid formation of ordered porous alumina by a hard anodizing procedure involving a powerful cooling stage and obtained an ultra-high aspect ratio (>1,000) of anodic porous alumina by anodizing in oxalic acid at 120-150...

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Section: Introductionmentioning

confidence: 99%

Fabrication of Anodic Porous Alumina by Squaric Acid Anodizing

Kikuchi¹,

Yamamoto²,

Natsui³

et al. 2014

Electrochimica Acta

View full text Add to dashboard Cite

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“…Four types of electrolytes based on the following inorganic acids have been reported to date for the fabrication of anodic porous alumina: sulfuric (H 2 SO 4 ) [25][26][27], phosphoric (H 3 PO 4 ) [28][29][30], chromic (H 2 CrO 4 ) [31][32][33], and selenic (H 2 SeO 4 ) [34] acid. Among these inorganic electrolytes, the use of sulfuric, phosphoric, and selenic acid for anodizing under suitable anodizing conditions results in the formation of highly ordered anodic porous alumina via self-ordering.…”

Section: Introductionmentioning

confidence: 99%

Fabrication of anodic porous alumina via anodizing in cyclic oxocarbon acids

Kikuchi

Nakajima

Kawashima

et al. 2014

Applied Surface Science

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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...

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“…However, the enrichment was only obvious at lower H 2 O concentrations, at which the formation voltage increased to higher than 100 V [8]. The H 2 O concentration-dependent enrichment of fluoride may be related to the mechanism of porous film growth, i.e., either field-assisted dissolution [17] or field-assisted flow [18,19]. The precise understanding of the growth mechanism is the subject of further study.…”

Section: Methodsmentioning

confidence: 96%