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ELECTROPLATED ALUMINUM FOR CORROSION CONTROL Gustavo R. Vallejo, Technical Sales Manager AlumiPlate, Inc.

, Minneapolis, MN

ABSTRACT Electroplated aluminum, a high purity aluminum plating, is commercially available for corrosion control. The coating can be applied via a wet but non-aqueous process to any conductive substrate, from carbon steel to aluminum beryllium alloys and even graphite. The process is compliant with existing military aluminum plating specifications and has been qualified by a number of OEM’s. High purity aluminum has excellent corrosion resistance properties, even as a thin coating. It is also highly ductile, nonembrittling, mitigates galvanic corrosion and can be used in applications up to 1,000 F. The coating is especially useful in the aerospace industry. The plating process will be introduced. Also several applications will be discussed including cadmium substitution, high-strength and embrittlement-sensitive components, elimination of galvanic corrosion with aluminum assemblies, and replacement of ion vapor deposited aluminum. INTRODUCTION In the world of surface finishing there is always a need for new innovations in corrosion coatings and unfortunately we have yet to find one coating that meets all (or even most needs). While there are a large number of surface coatings and treatments commercially available that offer adequate corrosion protection in many applications, there are specialty areas in the aircraft industry where the traditional suite of alternatives offer sub adequate solutions. New coatings are constantly being sought for improvement over previous compromise solutions, as well as to accommodate industry, environmental, or regulatory changes that occur from time to time. One such change that is affecting the aircraft industry is the ever-increasing regulatory and environmental pressure for the elimination of cadmium1. Aircraft manufacturers are evaluating a variety of alternatives, most of which are showing poor results for the wholesale replacement of cadmium. Electroplated aluminum has established itself in a wide variety of aerospace, defense and commercial applications as an ideal and higher performance coating alternative to cadmium. Electroplated aluminum is non toxic and non hazardous to the environment and eliminates the concerns for handling and disposal that exists in cadmium.

Metals Processing & Materials 40 CFR 438, final rule effective December 2002, substantially lowers the allowable limits of Cr, Cd, Zn, Ni and Sn in effluent water during fabrication or maintenance of aircraft. The Directive of the Council of European Communities COM (97) 358 calls for the elimination of Cd, Hexavalent Cr, Hg and Pb in transportation equipment.

Aluminum has long been recognized for its anti corrosion properties and has been applied as a surface treatment by a variety of coating technologies, none of which have proven themselves to be as effective, economical, scalable and flexible as electroplated aluminum. Electroplated aluminum is available commercially through AlumiPlate Inc. Hazardous Materials Elimination for Corrosion Resistance Cadmium, a regulated toxic material, is commonly applied to a wide variety of aircraft components for corrosion resistance. The aerospace industry has long sought a drop-in cadmium alternative. Organic and metallic coatings have been investigated. Most cannot match the corrosion resistance of an equally thick cadmium coating, requiring thicker coatings or a slight re-design for equivalent performance. The sheer volume of parts involved demands a significant effort to change drawing call outs, relax requirements or redesign the plated part. This fact has limited migration to green coatings. Electroplated aluminum, however, has the inherent corrosion resistance to provide equal or better performance than similar cadmium plating. Salt fog testing of thin deposits (12 micrometers) exceeds 1,000 hours of exposure in salt fog testing per ASTM B-117. Side-by-side salt-water exposure testing indicates aluminum can outperform cadmium in offshore or coastal environments (see Figure A).

Figure A Photographs of aluminum plated (right) versus cadmium plated steel coupons after 1,176 hours of environmental exposure testing to salt water (10 minute intervals per hour) at the U.S. Army South Florida Test Facility. Note the large dark area (rust) on the cadmium plated

coupon showing corrosion of the substrate2. The panels were plated with a minimum thickness of 12 micrometers and conversion coated. In addition, electroplated aluminum may help eliminate the need for hexavalent chromates. Chrome-based conversion coatings can enhance corrosion resistance in neutral pH chloride environments of thin cadmium coatings and Al alloys. Due to its superior resistance to attack, as-plated pure aluminum can provide adequate protection without the use of a conversion topcoat. Electroplated aluminum owes its superior corrosion resistance to several factors that interplay and complement each other. First, the coating is virtually free of impurities. Trace analysis and depth profiling testing confirm the layer is greater than 99.9% pure3. Impurities can act as corrosion initiation sites and limit the corrosion resistance of alloyed grades. Second, a thin, tenacious aluminum oxide layer protects the aluminum surface. The oxide layer acts as a barrier to further exposure of the aluminum surface to the attacking environment. In addition, pure aluminum instantaneously reforms the oxide layer if breached or scratched, passivating the surface. Fourth, the coating is fully dense and pore free. It is a true metallic barrier to corrosion of the substrate. The corrosive species cannot migrate to the substrate through cracks or voids in the coating. In mildly corrosive environments, this effect eliminates corrosion completely. Finally, pure aluminum is sacrificial to most conductive substrates. A pure aluminum coating over steels, SSTs, Fe-Ni alloys, Cu-based alloys and Al alloys preferentially protects the substrate in reducing O-, Cl-, F- and S- environments4. Combating Galvanic Corrosion Anytime dissimilar metals are in contact with each other in the presence of an electrolyte, current flows from the more noble (less electronegative or cathodic) to the less noble (more electronegative or anodic) material causing a decomposition of the anodic material. In essence, the anode dissolves at the expense of the cathode5. When aluminum is in contact with steel a similar galvanic effect results in corrosion. The proliferation of Al alloys in aerospace applications provides many opportunities for galvanic corrosion due to contact with steel, nickel, copper or titanium components.

Marlin Ritchie, Electroplated Aluminum: A Viable Replacement for Cadmium, presentation during U.S. Navy & Industry Corrosion Technology Exchange Conference, July 10, 2002, Louisville, KY.

TNO, Investigations of the Properties of Electrodeposited SIGAL Galvano Aluminum Coatings, TNO Metaalinstituut, Apeldoorn, Holland (1984). 4 Laque, F.L., Marine Corrosion Causes and Prevention Galvanic Series: Corrosion Potentials in Flowing Sea Water, John Wiley & Sons New York, NY 1975. West, John M., Basic Corrosion and Oxidation, 2nd Edition, Halsted Press, John Wiley & Sons, NY 1986.
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Electroplated aluminum can be used to combat galvanic corrosion. The process is applicable to all conductive substrates, including exotic materials like beryllium, aluminum-beryllium alloys, Fe-Ni super alloys, graphite, titanium and metal matrix composites. If any of these materials are in contact with aluminum components, they can be plated with a thin coating of pure Al to mitigate galvanic effects. Minimize Embrittlement Risks High strength steels are susceptible to hydrogen embrittlement (HE). HE lowers the toughness of the material, allowing a crack to initiate, propagate and grow to a critical size at stresses well below normal for that material6. Therefore, HE failures can happen at normally safe, operating stress levels and are often sudden or catastrophic. Waterbased plating processes, cadmium for instance, expose parts to hydrogen during activation and plating. Critical components are heat treated immediately after plating to diffuse the concentration of hydrogen in the material and limit embrittlement effects. The Industrial Fastener Institute recommends a hydrogen relief heat treatment of 23 hours at 375 F (425 F if parts cannot be treated within 4 hours of plating) for plated high strength aerospace fasteners7. Because of the insidious nature of HE, plating of flight safety critical components is avoided but has not been eliminated completely. Landing gear parts are routinely plated with cadmium, nickel and chromium and heat treated afterward. It is difficult to verify the integrity of the post plate heat treat and in some cases plating will be avoided for this reason in super critical parts. Electroplated aluminum virtually eliminates significant exposure of hydrogen to plated parts and has proven to be ideal for many critical components. There is some minor exposure to hydrogen during the pre-treatment (cleaning, strike layer deposition and activation). However, these steps are limited in duration and include inhibitors to control hydrogen evolution. During the aluminum plating step, parts cannot be embrittled. The electrolyte chemistry is aprotic8 (does not contain any free hydrogen) and therefore precludes the possibility of hydrogen exposure. Tensile and hydrogen embrittlement testing has shown the aluminum electroplating process to have no deleterious effects on mechanical properties. Many non-critical high strength steel parts go into field service after aluminum plating, without a subsequent heat treatment. Furthermore, the process can be configured to completely eliminate hydrogen exposure. For example, critical parts can be mechanically activated (blasted), and then re-activated via a non-aqueous process (such as plasma etching) before entering the aprotic aluminum plating step. This process is entirely devoid of hydrogen exposure and non-embrittling. Mitigate Environmentally Induced Cracking
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Dieter, George E., Mechanical Metallurgy, 3rd Edition, McGraw-Hill, NY 1986.

Industrial Fastener Institute, Standard IFI-142, Hydrogen Embrittlement Risk Management, Issued January 6, 1997. Lemkuhl, H, Mehler, K and Landau, Uwe, The Principles and Techniques of Electrolytic Aluminum Deposition and Dissolution in Organ-Aluminum Electrolytes, 1986.

High strength steels can experience delayed failure as a result of exposure to aqueous environments during assembly and service. Stress and corrosion combine to embrittle the material and lower its toughness. The propensity of a coated component to fail in the field is related to hydrogen embrittlement (HE) and hydrogen assisted stress cracking (HAC). HE and HAC decrease ductility (elongation and failure mode), reduce toughness (stress level needed to generate a crack) and lower fatigue strength (resistance to cracking under continuous levels of stress). The result is failure of a component at a stress level significantly below normal. Furthermore, the failure mode is brittle resulting in a sudden failure. Ductile failures are preferred, normally allowing enough time to discover cracking before complete failure occurs. Aluminum electroplated tensile specimens show a dimpled fracture surface characteristic of ductile failures. HAC is related to the enhancement of the propagation rate of an existing crack. For example, the presence of hydrogen decreases the corrosion resistance of fasteners under stress (i.e., a bolted joint) and increases the rate at which a crack would propagate through it. Decreased corrosion resistance leads to the formation of corrosion pits. These pits can develop micro cracks that grow at an accelerated rate. For coated components, the galvanic effect of the coating sacrificially protecting the substrate generates hydrogen. The rate of hydrogen evolution is related to the potential difference between the coating and the substrate. Both mechanisms feed on each other creating a vicious circle of higher stress leading to faster cracking leading to even higher stress. HAC effects can be determined by measuring the failure stress of coated specimens in salt water, while monitoring the electrical potential difference. Salt water contains many free Cl- H+ ions, which facilitate corrosion of the coating. Localized areas of the substrate eventually are exposed. At these areas, the coating and substrate are connected by the salt water (electrolyte) and a galvanic reaction occurs. The coating corrodes and protects the substrate. As it corrodes, hydrogen is evolved and may diffuse into the substrate. Where the potential difference between the coating and the substrate is large, the coating corrodes very quickly with accompanying high hydrogen generation rates. Therefore, specimens with sacrificial coatings that are not very corrosion resistant or that develop a large potential difference in salt water with the substrate, fail at strength levels below that of an uncoated component. Testing has shown that electroplated aluminum brings the lowest stress corrosion cracking susceptibility when compared to other coatings (Zn, Sn-Zn, Zn-Ni, Cd and Dacromet)9. Al electroplated components maintain their strength and toughness under stress and corrosion, and fail via the preferred ductile mode.

Heldt, Lloyd A., White, Calvin L., Zhang, Haidong, Susceptibility of Coated Steel Fasteners to Environment-Induced Failure, Michigan Technological University, December 1999.

Surface Anodization Electroplated aluminum is fully anodizeable. Since any conductive substrate can be electroplated, anodizing and other surface finishes exclusive to Al alloys are enabled onto steels, SSTs and Al-Be materials. Chromic, sulfuric and hardcoat anodize thickness are possible. The anodize process consumes the coating and grows the aluminum oxide layer at the same time. Plating thickness is varied according to desired anodize; 10 micrometers coatings are sufficient for chromic anodizing, 25-50 micrometer coatings may be required for hardcoats. Because of its high purity, the resultant anodize layer is quite pure and has optimum properties. Breakdown voltages of 1,000 volts per 25 micrometers of material are achievable. Surface hardness ranging HRC 65 70 per the Rockwell C Scale is common. Anodize layers can be colored by introducing dyes into its porous layers and then sealing the pores. The resultant finish is hard, uniform and resistant to ultraviolet light damage. Very deep and uniform black colorations are possible. Anodized aluminum exhibits excellent thermal conductivity while maintaining electrical insulation. Anodized electroplated aluminum is ideally suited for heat sinks, where thermal conductivity is desired but the surface must be electrically shielded.

Aluminum Coating and Plating Processes Currently Employed There are a variety of aluminum coating technologies available today, many of which are available commercially and are being employed in various specialty manufacturing environments. These are briefly described below, along with some mention to their suitability as a cadmium replacement in anti corrosion applications. Vacuum coatings Vacuum processes are available to deposit thin, pure coatings of aluminum (physical vapor deposition, chemical vapor deposition and ion vapor deposition). These processes are limited by their inherent line of sight nature. In general, resultant surfaces are somewhat porous. Ion vapor deposited aluminum is used for a variety of aerospace applications for corrosion resistance. The IVD Al coating process deposits a pure but porous Al layer. Densification via peening is often used to close the porosity and improve corrosion resistance. However, peening precludes coating of thin or fragile parts. IVD Al also suffers from geometry limitations due to its line of sight nature. Parts with intricate geometries or with critical inside surfaces that require coating cannot be coated

adequately with IVD Al. As a result of these process limitations, many parts that could benefit from a highly pure Al coating cannot be coated. Most parts presently coated with IVD are excellent candidates for aluminum electroplating. The process can be adapted to plate intricate geometries, inside surfaces and rounded components. Additionally, the dense electroplated layer does not require densification, thereby enabling plating of thin or fragile components sensitive to peening damage. Electroplated aluminum is also better suited for highly toleranced parts that do not allow thick coatings (25 micrometers or higher). Electroplated aluminum exceeds the corrosion resistance guidelines of a similar thickness of IVD Al by up to a factor of two10. A 12 micrometer thickness of electroplated Al can provide the same corrosion resistance as a 25 micrometer thickness of IVD Al. Thermal spray coatings Thermal spray processes have been used to deposit aluminum coatings. These coatings result in a porous, alloyed coating. Large irregularly shaped parts or components requiring field repair are best suited to thermal spraying. Mechanical bonding Mechanical bonding, explosive bonding and cladding techniques can affix pure aluminum grades (1199 or 1100) onto other stronger alloys. These techniques are optimum for large, flat surfaces.

The AlumiPlate Electroplating Process The aluminum electroplating process is similar to traditional electrochemical plating, the major exception being the enclosure of the plating line to create an oxygen free plating environment. Aluminum cannot be plated in a water-based bath. The commercially available plating process utilizes a solvent-based electrolyte and proprietary non-aqueous activation chemistry. To exclude water and oxygen, a nitrogen blanket under positive pressure covers the tanks inside the automated plating equipment (see Figure B).

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Fischer, Juergen and Fuhr, Bryan, Aluminum Plating Replaces Cadmium, Advanced Materials & Processes, Volume 155, Number 4, April 1999.

Figure B Long view of aluminum electroplating equipment, which houses a series of computer controlled activation, plating and rinsing tanks. The resultant electrodeposited aluminum coating has many properties ideally suited for aerospace applications. Case studies where electroplated aluminum is being used with success 1)Aerospace grounding straps 2)Electrical connectors 3)Aluminum Beryllium alloys Summary Electroplated aluminum is a viable engineering coating for a variety of aerospace applications including cadmium replacement, elimination of galvanic corrosion and mitigation of hydrogen embrittlement risks for high strength steels. It is proving itself in a variety of aircraft related applications and is available commercially.

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