SEMINAR TOPIC ON

Anodizing of Various Metals and Alloys

BE IV(MET.& MTRLS ENGG.)
METALLURGICAL & MATERIALS ENGINEERING DEPARTMENT FACULTY OF TECHNOLOGY AND ENGINEERING M.S UNIVERSITY OF BARODA VADODARA By: Ankur Shukla Roll no:945

Anodizing
Anodizing is an electrolytic passivation process used to increase the thickness of the natural oxide layer on the surface of metal parts. The process is called "anodizing" because the part to be treated forms the anode electrode of an electrical circuit.

Anodic films are most commonly applied to protect aluminum alloys, although processes also exist for titanium, zinc, magnesium, niobium, and tantalum.

Iron or carbon steel metal exfoliates when oxidized under neutral or alkaline micro electrolytic conditions; i.e., the iron oxide (actually "ferric hydroxide" or hydrated iron oxide, also known as rust) forms by anoxic anodic pits and large cathodic surface, these pits concentrate anions such as sulfate and chloride accelerating the underlying metal to corrosion.

Advantages
Anodizing increases corrosion resistance and wear resistance, and provides better adhesion for paint primers and glues than does 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.

 Preceding the anodization process, 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 bifloride 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 aluminum layer is grown by passing a direct current through an electrolytic solution, with the aluminum object serving as the anode (the negative electrode). The current releases hydrogen at the cathode (the positive 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.

Process ANODIZING OF ALUMINUM

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 30 to 300 amperes/meter (2.8 to 28 ampere/ft). Aluminum anodizing is usually performed in an acid solution which slowly dissolves the aluminum oxide. The acid action is balanced with the oxidation rate to form a coating with Nano pores, 10-150 nm in diameter. These pores are what allows the electrolyte solution and current to reach the aluminum substrate and continue growing the coating to greater thickness beyond what is produced by auto passivation. 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 micrometers for bright decorative work up to 150 micrometers for architectural applications.

Anodizing of other metals

Anodized magnesium Magnesium is anodized primarily as a primer for paint. A thin (5m) film is sufficient for this. Thicker coatings of 25m and up can provide mild corrosion resistance when sealed with oil, wax, or sodium silicate. Anodized zinc Zinc is rarely anodized, but a process was developed by the International Lead Zinc Research Organization .A solution of ammonium phosphate, chromate and fluoride with voltages of up to 200V can produce olive green coatings up to 80m thick. The coatings are hard and corrosion resistant.

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Anodized Tantalum
Tantalum anodizes in a similar fashion to titanium and niobium with a range of attractive colors being formed by interference at different film thicknesses. Again the film thickness is dependent on the anodizing voltage and typically ranges from 18-23 Angstroms per volt depending on electrolyte and temperature. Uses include Tantalum capacitors.

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 anodizing voltage. Uses include jewelry and commemorative coins.

Properties of Anodized Aluminum

Aluminum alloys are anodized to increase corrosion resistance, to increase surface hardness, and to allow dyeing (coloring), improved lubrication, or improved adhesion. The anodic layer is non-conductive. When exposed to air at room temperature, or any other gas containing oxygen, pure aluminum self-passivates by forming a surface layer of amorphous aluminum oxide 2 to 3 nm thick, which provides very effective protection against corrosion. Aluminum alloys typically form a thicker oxide layer, 5-15 nm thick, but tend to be more susceptible to corrosion. Aluminum alloy parts are anodized to greatly increase the thickness of this layer for corrosion resistance. The corrosion resistance of aluminum alloys is significantly decreased by certain alloying elements or impurities: copper, iron, and silicon,[5] so 2000, 4000, and 6000-series alloys tend to be most susceptible.

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Although anodizing produces a very regular and uniform coating, microscopic fissures in the coating can lead to corrosion. Further, the coating is susceptible to chemical dissolution in the presence of high and low pH chemistry, which results in stripping the coating and corrosion of the substrate. To combat this, various techniques have been developed either to reduce the number of fissures or to insert more chemically stable compounds into the oxide, or both. For instance, sulfuric anodized articles are normally sealed, either through hydro-thermal sealing or precipitating sealing, to reduce porosity and interstitial pathways that allow for corrosive ion exchange between the surface and the substrate. Precipitating seals enhance chemical stability but are less effective in eliminating ion exchange pathways. Some aluminum aircraft parts, architectural materials, and consumer products are anodized. Anodized aluminium 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.

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Although anodizing only has moderate wear resistance, the deeper pores can better retain a lubricating film than a smooth surface would. Anodized coatings have a much lower thermal conductivity and coefficient of linear expansion than aluminium. As a result, the coating will crack from thermal stress if exposed to temperatures above 80 C. The coating can crack, but it will not peel. The melting point of aluminum oxide is 2050 C, much higher than pure aluminums 658 C. (This can make welding more difficult.) In typical commercial aluminum anodization processes, the aluminum oxide is grown down into the surface and out from the surface by equal amounts. So anodizing will increase the part dimensions on each surface by half of the oxide thickness. For example a coating that is (2 m) thick, will increase the part dimensions by (1 m) per surface. If the part is anodized on all sides, then all linear dimensions will increase by the oxide thickness. Anodized aluminum surfaces are harder than aluminum but have low to moderate wear resistance, although this can be improved with thickness and sealing.

DYEING USING ANODIZING

Colored iPod Mini cases are dyed following anodization and before thermal sealing

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The most common anodizing processes, for example sulfuric acid on aluminum, 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 aluminum-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 commonly used 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. Splash effects are created by dying the unsealed porous surface in lighter colors and then splashing darker color dyes onto the surface.

Aqueous and solvent based dye mixtures may also be alternately applied since the colored dyes will resist each other and leave spotted effects.

Printing

Photo quality images and graphics in vivid color may be printed into the unsealed porous oxide layer using color dyes via silkscreen, sublimation transfer or digital printer. Line art quality graphics can be achieved by use of a printer. Color graphics may also be directly applied by hand using an airbrush, sponge or paintbrush. Printed anodizing is sealed to prevent or reduce dye bleed out. Uses include baseball bats, signs, furniture, surgical trays, motorcycle components, and architectural molding.

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%.[6] 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.

Cleaning
Anodized aluminums surfaces are susceptible to Panel Edge Staining, a unique type of surface staining that can affect the structural integrity of the metal.

Environmental impact
Anodizing is one of the more environmentally friendly metal finishing processes. With the exception of organic (aka integral color) anodizing, the by-products do not contain heavy metals, halogens or volatiles. The most common anodizing effluents, aluminum hydroxide and aluminum sulfate, are recycled for the manufacturing of alum, baking powder, cosmetics, newsprint and fertilizer or used by industrial wastewater treatment systems

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. Alternatively, special oversize taps may be used to pre compensate 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.