Anodizing

  Anodizing, or anodising, is an electrolytic passivation process used to increase the thickness of the natural oxide layer on the surface of metal parts. This process is of no use on carbon steel because rust puffs up and flakes off, constantly exposing new metal to corrosion. But on many other metals, anodizing increases corrosion resistance and wear resistance, and provides better adhesion for paint primers and glues than bare metal. Anodic films can also be used for a number of cosmetic effects, either with thick porous coatings that can absorb dyes or with thin transparent coatings that add interference effects to reflected light. Anodizing is also used to prevent galling of threaded components and to make dielectric films for electrolytic capacitors. Anodization changes the microscopic texture of the surface and can change the crystal structure of the metal near the surface. Coatings are often porous, thick ones inevitably so, so a sealing process is often needed to achieve corrosion resistance. The process derives its name from the fact that the part to be treated forms the anode portion of an electrical circuit in this electrolytic process. Anodic films are generally much stronger and more adherent than most paints and platings, making them less likely to crack and peel. Anodic films are most commonly applied to protect aluminium alloys, although processes also exist for titanium, zinc, magnesium, and niobium.

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History

Anodizing was first used on an industrial scale in 1923 to protect Duralumin seaplane parts from corrosion. This early chromic acid process was called the Bengough-Stuart process and was documented in British defence specification DEF STAN 03-24/3. It is still used today despite its legacy requirements for a complicated voltage cycle now known to be unnecessary. Variations of this process soon evolved, and the first sulfuric acid anodizing process was patented by Gower and O'Brien in 1927. Sulfuric acid soon became and remains the most common anodizing electrolyte.^[1]

Oxalic acid anodizing was first patented in Japan in 1923 and later widely used in Germany, particularly for architectural applications. Anodized aluminum extrusion was a popular architectural material in the 1960's and 1970's, but has since been displaced by cheaper plastics and powder paint.^[2] The phosphoric acid processes are the most recent major development, so far only used as pretreatments for adhesives or organic paints.^[1] A wide variety of proprietary and increasingly complex variations of all these anodizing processes continue to be developed by industry, so the growing trend in military and industrial standards is to classify by coating properties rather than by process chemistry.

Anodized aluminum

Aluminum alloys are anodized to increase corrosion resistance, to increase surface hardness, and to allow dyeing, improved lubrication, or improved adhesion.

When exposed to the atmosphere at room temperature, pure aluminum self-passivates by forming a surface layer of amorphous aluminum oxide 2 to 3 nm thick^[3] which provides very effective protection against corrosion. Aluminum alloys typically form a thicker oxide layer, 5-15 nm thick, but tend to be more prone to corrosion. Aluminum alloy parts are anodized to greatly increase the thickness of this layer for corrosion resistance. Copper, iron, and silicon alloying elements or impurities degrade corrosion resistance significantly,^[4] so 2000, 4000, and 6000-series alloys tend to be most susceptible. Most aluminum aircraft parts, architectural materials, and consumer products are anodized. Anodized aluminum can be found on mp3 players, flashlights, cookware, cameras, sporting goods, window frames, roofs, in electrolytic capacitors, and on many other products both for corrosion resistance and the ability to retain dye. Although anodizing only has moderate wear resistance, the deeper pores can better retain a lubricating film than a smooth surface would. For example, the cylinders of a modern BMW aluminum V8 cylinders have no loose liner: instead, the walls are hard anodized. This complicates a reboring operation (although not common, given the longevity of modern engines due to improved lubricants), as the hard coating must be restored if the block is rebored. (Earlier liner-free aluminum block designs use specific aluminum alloys, with softer components chemically etched away to expose the harder portions of the mixed crystal structure.)

Anodized coatings have a much lower thermal conductivity and coefficient of linear expansion than aluminum. As a result, they will crack if exposed to temperatures above 80°C, although they will not peel.^[5] Their melting point is 2050°C, much higher than pure aluminum's 658°C.^[5] This can make welding more difficult. In typical commercial processes, the aluminum oxide coating is grown from and into the surface of the aluminum in about equal amounts, so for example a 2μm thick coating will only increase part dimensions by 1μm per surface. Anodized aluminum surfaces are harder than aluminum but have low to moderate wear resistance, although this can be improved with thickness and sealing.

Before being anodized, wrought alloys are cleaned in either a hot soak cleaner or in a solvent bath and may be etched in sodium hydroxide (normally with added sodium gluconate), ammonium bifluoride or brightened in a mix of acids. Cast alloys are normally best just cleaned due to the presence of intermetallic substances unless they are a high purity alloy such as LM0.

The anodized aluminium layer is grown by passing a direct current through an electrolytic solution, with the aluminum object serving as the anode (the positive electrode). The current releases hydrogen at the cathode (the negative electrode) and oxygen at the surface of the aluminum anode, creating a build-up of aluminum oxide. Alternating current and pulsed current is also possible but rarely used. The voltage required by various solutions may range from 1 to 300 V DC, although most fall in the range of 15 to 21 V. Higher voltages are typically required for thicker coatings formed in sulfuric and organic acid. The anodizing current varies with the area of aluminum being anodized, and typically ranges from 0.3 to 3 amperes of current per square decimeter (15.5 square inches).

Aluminium anodizing is usually performed in an acid solution which slowly disolves the aluminum oxide. The acid action is balanced with the oxidation rate to form a coating with microscopic pores, 10-150 nm in diameter.^[5] These pores are what allows the electrolyte solution and current to reach the aluminium substrate and continue growing the coating to greater thickness beyond what is produced by autopassivation.^[6] However, these same pores will later permit air or water to reach the substrate and initiate corrosion if not sealed. They are often filled with colored dyes and/or corrosion inhibitors before sealing. Because the dye is only superficial, the underlying oxide may continue to provide corrosion protection even if minor wear and scratches may break through the dyed layer.

Conditions such as electrolyte concentration, acidity, solution temperature, and current must be controlled to allow the formation of a consistent oxide layer. Harder, thicker films tend to be produced by more dilute solutions at lower temperatures with higher voltages and currents. The film thickness can range from under 0.5 micrometres for bright decorative work up to 150 micrometres for architectural applications.

The most widely used anodizing specification, MIL-A-8625, defines three types of aluminum anodization. Type I is Chromic Acid Anodization, Type II is Sulphuric Acid Anodization and Type III is sulphuric acid hardcoat anodization. Other anodizing specifications include MIL-A-63576, AMS 2469, AMS 2470, AMS 2471, AMS 2472, AMS 2482, ASTM B580, ASTM D3933, ISO 10074 and BS 5599. AMS 2468 is obsolete. None of these specifications define a detailed process or chemistry, but rather a set of tests and quality assurance measures which the anodized product must meet. BS 1615 provides guidance in the selection of alloys for anodizing. For British defence work, a detailed chromic and sulfuric anodizing processes are described by DEF STAN 03-24/3 and DEF STAN 03-25/3 respectively.

Chromic Acid Anodizing

The oldest anodizing process uses chromic acid. It is widely known as Type I because it is so designated by the MIL-A-8625 standard, but it is also covered by AMS 2470 and MIL-A-8625 Type IB. Chromic acid produces thinner, (0.00002" to 0.0007" or 0.5 μm to 18 μm)^[7] more opaque films that are softer, ductile, and to a degree self-healing. They are harder to dye and may be applied as a pretreatment before painting. The method of film formation is different from using sulfuric acid in that the voltage is ramped up through the process cycle.

Sulfuric Acid Anodizing

Sulfuric acid is the most widely used solution to produce anodized coating. Coatings of moderate thickness (0.00007" to 0.001" or 1.8 μm to 25 μm)^[7] are known as Type II, as named by MIL-A-8625, while coatings thicker than 0.001" are known as Type III, hardcoat, or engineered anodizing. Very thin coatings similar to those produced by chromic anodizing are known as Type IIB. Thick coatings require more process control,^[5] and are produced in a refrigerated tank near the freezing point of water with higher voltages than the thinner coatings. Hard anodizing can be made between (25 and 150μm 0.001" to 0.006") thick. Anodizing thickness increases wear resistance, corrosion resistance, ability to retain lubricants, and electrical and thermal insulation. Standards for thin sulfuric anodizing are given by MIL-A-8625 Types II and IIB, AMS 2471 (undyed), and AMS 2472 (dyed). Standards for thick sulfuric anodizing are given by MIL-A-8625 Type III, AMS 2469, BS 5599, BS EN 2536 and the obsolete AMS 2468 and DEF STAN 03-26/1.

Organic acid anodizing

Anodizing can be carried out in organic acids such as oxalic acid to produce integral colors from pale yellow to deep bronze in the anodized coating without dyes.^[5] The shade of color produced is sensitive to variations in the metallurgy of the underlying alloy and cannot be reproduced consistently.^[2] Thicknesses up to 50μm can be achieved. Organic acid anodizing is called Type IC by MIL-A-8625.

Phosphoric acid anodizing

Anodizing can be carried out in phosphoric acid, usually as a surface preparation for adhesives. This is described in standard ASTM D3933

Borate and Tartrate Baths

Anodizing can also be performed in Borate or Tartrate Baths in which aluminum oxide is insoluble. In these processes, the coating growth stops when the part is fully covered, and the thickness is linearly related to the voltage applied.^[5] These coatings are free of pores, relative to the sulfuric and chromic acid processes.^[5] This type of coating is widely used to make electrolytic capacitors, because the thin aluminium films (typically less than 0.5 μm) would risk being pierced by acidic processes.^[1]

Plasma electrolytic oxidation

Plasma electrolytic oxidation is a similar process, but where higher voltages are applied. This causes sparks to occur, and results in more crystalline type coatings.

Other metals

Anodized titanium

Anodized titanium is used in a recent generation of dental implants. Anodizing generates a thicker layer of titanium dioxide (>1 µm and up to >2.5 µm compared with much less than 1 µm for un-anodized specimens)^{[citation needed]} and a characteristic surface topography.^{[citation needed]} It has been suggested that both of these parameters improve the performance—longevity, stability—of dental implants, but the technology is still new and there are not yet clear clinical data to support these claims.^{[citation needed]}

Titanium anodic films cannot be made thicker than about 300nm, and are therefore susceptible to mechanical damage.^[8] Standards for titanium anodizing are given by AMS 2487 and AMS 2488.

Anodizing titanium generates an array of different colors without dyes, for which it is sometimes used in art, costume jewelry, body piercing jewelery and wedding rings.[2][3] The color formed is dependent on the thickness of the oxide (which is determined by the anodising voltage); it is caused by the interference of light reflecting off the oxide surface with light traveling through it and reflecting off the underlying metal surface. Titanium nitride coatings can also be formed, which have a brown or golden color and have the same wear and corrosion benefits as anodization.

Anodized Magnesium

Magnesium is anodized primarily as a primer for paint. A thin (5μm) film is sufficient for this.^[8] Thicker coatings of 25μm and up can provide mild corrosion resistance when sealed with oil, wax, or sodium silicate.^[8] Standards for magnesium anodizing are given in AMS 2466, AMS 2478, AMS 2479, and ASTM B893.

Anodized Zinc

Zinc is rarely anodized, but a process was developed by the International Lead Zinc Research Organization and covered by MIL-A-81801.^[8] A solution of ammonium phosphate, chromate and fluoride with voltages of up to 200V can produce olive green coatings up to 80μm thick.^[8] The coatings are hard and corrosion resistant.

Anodized niobium

Niobium anodizes in a similar fashion to titanium with a range of attractive colors being formed by interference at different film thicknesses. Again the film thickness is dependent on the anodising voltage. Uses include jewelry and commemorative coins.

Dyeing

The most common anodizing processes, for example sulfuric acid on aluminium, produce a porous surface which can accept dyes easily. The number of dye colors is almost endless; however, the colors produced tend to vary according to the base alloy. Though some may prefer lighter colors, in practice they may be difficult to produce on certain alloys such as high-silicon casting grades and 2000-series copper alloys. Another concern is the lightfastness of organic dyestuffs—some colors (reds and blues) are particularly prone to fading. Black dyes and gold produced by inorganic means (ferric ammonium oxalate) are more lightfast. Dyed anodizing is usually sealed to reduce or eliminate dye bleed out.

Alternatively, metal (usually tin) can be electrolytically deposited in the pores of the anodic coating to provide colors that are more lightfast. Metal dye colors range from pale champagne to black. Bronze shades are preferred for architectural use.

Alternatively the color may be produced integral to the film. This is done during the anodizing process using organic acids mixed with the sulfuric electrolyte and a pulsed current.

Sealing

Acidic anodizing solutions produce pores in the anodized coating. These pores can absorb dyes and retain lubricants, but are also an avenue for corrosion. When lubrication properties are not critical, they are usually sealed after dyeing to increase corrosion resistance and dye retention. Long immersion in boiling-hot deionized water or steam is the simplest sealing process, although it is not completely effective and reduces abrasion resistance by 20%.^[5] The oxide is converted into its hydrated form, and the resulting swelling reduces the porosity of the surface. Cold sealing, where the pores are closed by impregnation of a sealant in a room-temperature bath, is more popular due to energy savings. Coatings sealed in this method are not suitable for adhesive bonding. Teflon, nickel acetate, cobalt acetate, and hot sodium or potassium dichromate seals are commonly used. MIL-A-8625 requires sealing for thin coatings (Types I and II) and allows it as an option for thick ones. (Type III)

Mechanical considerations

Anodizing will raise the surface, since the oxide created occupies more space than the base metal converted. This will generally not be of consequence except in the case of small holes threaded to accept screws. Anodizing may cause the screws to bind, thus the threaded holes may need to be chased with a tap to restore the original dimensions. Alternately, special oversize taps may be used to precompensate for this growth. In the case of unthreaded holes that accept fixed diameter pins or rods a slightly oversized hole to allow for the dimension change may be appropriate.

References

1. ^ ^{a b c} Sheasby, P. G. & Pinner, R. (2001), , , vol. 1 (sixth ed.), Materials Park, Ohio & Stevenage, UK: ASM International & Finishing Publications, p. 427-596, ISBN 0-904477-23-1
2. ^ ^{a b} Sheasby, P. G. & Pinner, R. (2001), , , vol. 2 (sixth ed.), Materials Park, Ohio & Stevenage, UK: ASM International & Finishing Publications, p. 597-742, ISBN 0-904477-23-1
3. ^ Sheasby, P. G. & Pinner, R. (2001), , vol. 1 (sixth ed.), Materials Park, Ohio & Stevenage, UK: ASM International & Finishing Publications, p. 5, ISBN 0-904477-23-1
4. ^ Sheasby, P. G. & Pinner, R. (2001), , vol. 1 (sixth ed.), Materials Park, Ohio & Stevenage, UK: ASM International & Finishing Publications, p. 9, ISBN 0-904477-23-1
5. ^ ^{a b c d e f g h} Edwards, Joseph (1997). Coating and Surface Treatment Systems for Metals. Finishing Publications Ltd. and ASM International, pp. 34-38. ISBN 0-904477-16-9. 
6. ^ Sheasby, P. G. & Pinner, R. (2001), , , vol. 1 (sixth ed.), Materials Park, Ohio & Stevenage, UK: ASM International & Finishing Publications, p. 327-425, ISBN 0-904477-23-1
7. ^ ^{a b} US Military Specification MIL-A-8625, ASSIST database
8. ^ ^{a b c d e} Edwards, Joseph (1997). Coating and Surface Treatment Systems for Metals. Finishing Publications Ltd. and ASM International, pp. 39-40. ISBN 0-904477-16-9.