Low Voltage Processes for Hard Anodizing of Aluminum
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1 Low Voltage Processes for Hard Anodizing of Aluminum Leonid Lerner, Tim Cabot Sanford Process Corporation 1
2 Low Voltage Processes for Hard Anodizing of Aluminum Leonid Lerner, Tim Cabot Sanford Process Corporation The Sanford Process TM had its beginning in California and was the invention of Paul Sanford. Hardcoating of aluminum by customary processes always presented difficulties when alloys of high impurity were processed. This was particularly true when alloys containing significant amounts of copper - 3.5% to 4.0% - were processed. Catastrophic dissolution, called burning led processors to avoid these alloys, or at a minimum, imposed limitations on the hardcoat thickness to less than 2 mils (50 microns). Even then extreme care was necessary and results were uncertain. Paul Sanford, in collaboration with John Franklin, invented an additive called Sanfran TM which, in combination with a modified electrolyte, not only eliminated burning on high copper and other difficult alloys of aluminum, but also improved the quality of the hardcoat film. Additionally, with the new electrolyte it was possible to form thicker coatings. The process utilized pure DC current at voltages up to 100 volts with a current density up to 40 amperes per square foot. This process is known as the Classic Sanford Process TM (High Voltage DC). It was used extensively to process components for the aircraft industry. Sanford Process Corporation continued developing products and techniques in the anodizing and hardcoat industry. Its Sanford Hardlube TM is a Teflon dispersion treatment that was perfected as a post 2
3 treatment for Sanford Hardcoat. Sealing techniques were studied and improved. Sanford was rapidly becoming recognized worldwide for its superior hardcoat system, technical expertise, and process know-how, and continued research and development of the quality of hard anodic films. Sanford Process Corporation does not operate a job shop nor does it do any commercial hardcoating, but is affiliated with a large independent hard anodizing shop - Duralectra CHN, LLC which provides Sanford Process Corporation with the world s largest experimental facility for field testing and proving - or disproving - Sanford s innovations. The ability to test under actual job shop conditions has been an invaluable asset in the development of new ideas by Sanford Process Corporation. Low Voltage DC+AC Sanford Processes Sanford s management realized that continued leadership by the company depended on continuous improvement. A research team was assembled and several long-range objectives were outlined, most important of which was development of a more efficient power supply for hardcoating of aluminum. Years of research were invested in this project. Many prototypes were built, tested, and discarded, but each brought the team closer to its goal. Finally, after 4 years of constant painstaking research, during which time four new patents were awarded, the company developed a low voltage power supply, which superimposes AC current on DC in the anodizing process. The new process is called the Sanford Plus Process TM. The combination of the DC+AC in the low voltage power supply (0-18 volts DC vs volts in high voltage DC systems) with the additive Sanfran TM (additive) makes it possible to hardcoat any aluminum alloy while maintaining exacting quality control during the process. In 1986, Sanford Process Corporation introduced a new process Sanford Quantum Process TM, which is a low voltage (average 12 VDC) hardcoating process in room temperature (70ºF) with the possibility of creating up to micron of coating while meeting the Mil spec abrasion resistance 3
4 requirements. The coatings have lighter colors, are more uniform and demonstrate higher abrasion resistance than those formed at high DC voltages and low temperatures. The Sanford Quantum Process is most popular with color hard anodizing applications. Thanks to a colorless appearance of the oxide film, possibility of bright color hardcoat is a new opportunity for different applications. Sanford Low Voltage DC+AC Processes Vs. Conventional High Voltage DC Process For years the industry standard for aluminum hardcoating has been the use of high voltage power processes with very few variations. Anodizers became complaisant with the standard techniques used throughout the industry and rarely looked to improve the processes used. One of the main reasons for this was that companies didn t have the ability or knowledge to change a process that had been proven over many years of use. But Sanford Process Corp. was and still is one of the few companies in the industry trying to improve existing techniques and develop new and innovative ways to hardcoat aluminum. During the hard anodize process, aluminum parts are subjected to high electrical current densities for the creation of the hard anodize oxide. This process generally creates polarization of the cathode and anode in the electro-chemical process; this generates large amounts of oxygen at the anode and hydrogen at the cathode. This polarization fills the pores of the oxide coating and builds resistance to the electrical current. As a result, in conventional hard anodizing, progressively more voltage has to be applied in order to maintain adequate current densities. These high voltages generate dangerously high temperatures and the potential for catastrophic dissolution of parts being hard anodized. In order to avoid this damage, the 4
5 heat has to be removed with energy-intensive chillers. As a result of these two factors, energy bills for hardcoating are substantial. However, with the Sanford Process and the use of the additive Sanfran, burning of parts is almost eliminated, and the unique use of DC + AC current is believed to disperse the polarization effect and permit significant advantages to be achieved. These advantages include the capability of hard anodizing all aluminum alloys, higher abrasion resistance, superior coating hardness and uniformity (see Fig. 7), higher thermal conductivity and corrosion resistance, and the ability to dye with bright vibrant colors, among other things. It was believed for years that in order to successfully hardcoat aluminum very high voltages were needed. These voltage levels reached 60 to 100 volts DC. It was also believed that in order to create thick coatings and avoid burning parts, temperature levels had to be as low as 25-32ºF. But as Sanford Process developed their technology, it was realized that with the Sanford Low Voltage technology, successful hardcoating could be achieved with as little as 11 to 20 volts DC, plus an AC component. The AC regularly reverses direction, creating a windshield wiper effect that wipes oxygen created on the plus electrode and hydrogen created on the minus electrode. DC current flows easier and tank voltage is reduced drastically. DC energy consumption is reduced proportionally. And, depending upon the process, temperatures could be maintained at 40-50ºF (Sanford Plus ) and 65-72ºF (Sanford Quantum ). The results were beyond what conventional hardcoating had achieved before, and soon significant advantages were realized with the use of the Sanford technology. Sanford Quantum vs. Sanford Plus 1. Electrolyte Temperature Sanford Quantum Process: 70ºF and higher Sanford Plus Process: 40-50ºF 5
6 2. Thickness Sanford Quantum Process: Up to mils Sanford Plus Process: Up to 5-7 mils, depending on the alloy 3. Color Sanford Quantum Process: Light a good base for dyeing bright colors Sanford Plus Process: Much darker color 4. Abrasion Resistance Sanford Quantum Process and Sanford Plus Process are the same 5. Energy Consumption Sanford Quantum Process is less than Sanford Plus Process; When looking at graphs of the amounts of current and voltage used over time during each of the types of hard anodizing processes, it becomes apparent the amount of energy conservation available through the Sanford Hard-Anodize Processes. During a standard hard-anodize run the amount of current used peaks, then drops to its origin point after a certain amount of time. During a Sanford Process run, the amount of current used peaks, then tails off very slowly, never actually reaching its point of origin. This allows the operator to run parts for extended periods of time, giving more uniform and thicker coatings, without having to monitor or increase current as the process progresses. Similarly, when comparing voltage use between conventional hard-anodizing and the Sanford Process, we are able to see a significant difference between the voltage levels of each process. During a conventional high-voltage hard-anodize run, the voltage level is increased in a linear manner until the process is complete, reaching levels up to and sometimes going above 100 VDC. During the Sanford Process, however, voltages rarely go above 20 VDC and maintain stable levels throughout the process, thus allowing little monitoring once the process level is reached. (See Appendix 1) 6
7 ELECTROLYTE COMPOSITIONS FOR SANFORD HARD ANODIZING PROCESSES Sanford Plus Sanford Plus Process is distinguished by the settings of electrolyte temperatures: 45º F (7.2º C) for all alloys accepts 2000 series. 50º F (10º C) for 2000 series; Electrolyte Concentration Sulfuric acid: 300 +/- 6 g/l. Additive: 1/3 of the volume of concentrated sulfuric acid used. Aluminum g/l (titer 0.6 2) Sanford Salvage - PROCESS FOR EXTREMELY THICK COATINGS Sanford Salvage Process can provide coatings up to 6-7 mils ( microns) on most aluminum alloys including 6000 series alloys. To produce these coatings a more diluted concentration of electrolyte is required. Electrolyte Concentration Sulfuric acid: 200 +/- 6 g/l. Additive: 1/3 of the volume of concentrated sulfuric acid used. Aluminum g/l (titer 0.6 2). Electrolyte Temperature: 40ºF (4.5ºC) or lower. Sanford Quantum Sanford Quantum Process is a DC+AC hard-anodizing process, which is distinguished by the following setting of the electrolyte temperature: 70ºF (21ºC) for all alloys. Electrolyte Concentration Sulfuric acid: 300 +/- 6 g/l. Additive: 1/3 of the volume of concentrated sulfuric acid used. Aluminum: g/l (titer 0.6 2). 7
8 High Voltage DC (Sanford Classic ) High Voltage DC process can provide coatings up to 3 mils (75 microns) on most aluminum alloys. Electrolyte Concentration Sulfuric acid: 300 +/- 6 g/l. Additive: 1/3 of the volume of concentrated sulfuric acid used. Aluminum: g/l (titer 0.6 2). Electrolyte Temperature: 32ºF (0ºC) or lower. Sanford Hardlube The Process provides a low coefficient of friction to hardcoating. Sanford Hardlube (a combination of Teflon* and any of Sanford Hardcoat Processes) provides great lubricity and a non-stick surface along with the high abrasion and corrosion resistance of Sanford Hardcoating. Friction of the hard anodizing surface can be lowered by fivefold. Fig.1 8
9 The most noticeable feature in Low Voltage Process is the uniformity of the oxide coating. Uniformity is chronological from the fact that the anodizing voltage does not change during a major portion of the anodizing cycle. The distance between the pores in an oxide film is proportional to the applied voltage. This means that the higher the anodizing voltage, the fewer pores per unit of surface area will be formed. In the Low Voltage DC+AC Processes, the maximum voltage is reached during a short period and then the voltage stays almost constant. The major part of the coating is formed during the time when the voltage is steady. The major part of the coating is uniform and has homogeneous porosity. This exterior layer had been formed before the maximum voltage level was reached (it should be remembered that the film is growing from underneath, where the combining of aluminum and oxygen occurs see fig. 2) 30 years ago the Boeing Commercial Airplane Co. program launched the program to find the hard anodizing process, which might form a pit-free hardcoating. In spite of being hard and meeting the Military Specifications as to Abrasion Resistance requirement, hard oxide films on heavily alloyed aluminum often have internal cavities called pits. These pits are very conspicuous above a certain thickness on some alloys, as seen in the photographs on fig. 5. A pit exposes itself whenever the oxide film is honed to remove the outer surface. Uniformity of hard oxide film after Sanford Low Voltage Process Fig. 7 9
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11 a) b) Fig.5 Cross section of oxide film formed by the High Voltage Process at 29ºF (Sanford Classic Process TM ) a) 2024 alloy, 2.7 mil; b) 7075 alloy, 3.5 mil.1-aluminum; 2-oxide film; 3- plastic medium A number of aluminum panels 4 x 6 x.04 of 7075 and 2024 alloys were sent from the Boeing Co. to various hard-anodizing shops in this country, employing different anodizing processes. These shops were requested to provide the panels with and 5-6 mils of coatings. In our company these panels were anodizing both with the Low Voltage and High Voltage processes. Fig. 6 demonstrates that the new process dramatically diminishes the possibility of creating pits on 2024 and 7075 alloys, not only at 3 mils thickness, but at 6 mils as well. 11
12 a) b) c) d) Fig.6 Cross section of the oxide film formed by Low Voltage Process (Sanford Plus TM ) a) 2024 alloy, 2.6 mil, 40ºF; b) 2024 alloy, 5.7 mil, 50ºF; c) 7075 alloy, 3.1 mil, 40ºF; d) 7075, 5.6 mil, 40ºF. 1-aluminum; 2-oxide film; 3-plastic medium 12
13 The Low Voltage Processes provides higher abrasion resistance. For thicknesses of 2-3 mils, Sanford Plus Process demonstrates about half the weight loss normally observed after 10,000 revolutions for High Voltage Process oxide films. However, at thicknesses ranging from 4 to 6 mils, the difference in abrasion test results becomes even more dramatic. The relationship of weight loss with Low Voltage coating thicknesses is shown on fig. 3 for 7075, 6061 and 2024 alloys limit Weight Loss, mg 6061, 7075 limit Thickness, mil Fig. 3 It has been commonly recommended that parts to be anodized should have rounded edges rather than sharp ones to avoid a so-called edge-defect. Normally, at thicknesses more than 2 mils, the oxide film at the edge expands and becomes susceptible to mechanical destruction. Oxide films produced by the Sanford Plus Process is significantly less vulnerable to destruction because of the following two reasons: 13
14 1. The oxide film is much more uniform and leaves a clean edge. 2. The low voltage-anodized oxide film is much more porous more ductile and less brittle. The above discussed properties such as higher hardness, less pronounced edge-defect, and lesser number of pits may be considered as a consequence of the uniformity of the oxide film. The uniformity, in its turn, is sequential from the voltage being kept constant during a major portion of the anodizing cycle. A number of other advantages follow from the fact that the hard anodizing voltage is low. Among these properties we may name lower consumption of Faraday electricity and elimination of burning. As was mentioned above, the low voltage oxide film produced in strong electrolytes, such as sulfuric acid, is porous. The pores are very fine and do not necessarily diminish the hardness of the film built of aluminum oxide. Even when the volume occupied by pores is rather high, reaching 40-60% of the whole coating volume, the structure of the oxide film is still very strong to abrasion. Porosity increases when anodizing voltage diminishes. It means that employment of a much lower anodizing voltage in the Low Voltage Sanford Processes, as compared to the High Voltage Process, brings more porous oxide films which are more ductile, less susceptible to cracking when bent and with greater ability to color dye. High magnesium content alloys are reluctant to yield very thick oxide films during hard anodizing. If High Voltage Process is used, the maximum thickness for 6061 alloy temper T6 does not exceed mils. The Low Voltage Salvage Process allows production of much thicker oxide film on the same alloy. 6 and even 7 mil-thick-films may be anodized after a reasonable period of time (see fig. 4) and these coatings are still hard (see fig. 3). 14
15 At 12VDC in Sanford Quantum Process and 18VDC in Sanford-PlusProcess the current density may go up to ASF depending on alloy. That is why the speed of anodizing may reach about 1 mil per 8 min for the first mils. For higher thickness this rate slows down. Graph on fig. 4 illustrates the dependence of the low-voltage anodizing time upon coating thickness for the three alloys 2024, 6061 and The behaviors of current and voltage during the procedure in High Voltage Hard Anodizing Process vs. Low Voltage Hard Anodizing process see in self explanatory Appendix 1. Anodizing Time, min Thickness, mil Fig. 4 15
16 Appendix 1 TIME CURRENT CURRENT TIME 16
17 VOLTAGE VOLTAGE TIME TIME 17
18 The cross-section of oxide film after Sanford Low Voltage Process CONCLUSION Low voltage hard anodizing processes produced more uniform, very thick oxide with higher abrasion resistance, less pronounced edge-defect and more porous and ductile hard oxide film. The Sanford Low Voltage DC+AC Processes are simple and safe to operate. REFERENCES 1. M. Lerner, J. Morse, Sanford Process Corporation Hard- Anodizing of Aluminum Alloy by Low Voltage. 2. L. Lerner Multifunctional Power Supply for Different Hard Anodizing Processes and Applications 3. Sanford Process Instruction Manual To the memory of Dr. Moisey Lerner inventor of Sanford Low Voltage AC+DC Hard Anodizing Process, also my mentor and friend, dedicated this article. 18
19 Biographical Sketches Leonid M. Lerner Sanford Process Corporation One Shorr Court, Woonsocket, RI USA. Education: MS in Hydro-technical Engineering Work experience: for the past 29 years has been with Sanford Process Corporation as an Assistant to the Director of R&D, Project Manager, Engineering Manager, General Manager /Executive Vice President and President. He was involved in hard anodizing of aluminum and research, development, testing and installation of Low Voltage DC+AC Power Supplies. Tim Cabot Sanford Process Corporation One Shorr Court, Woonsocket, RI USA. Tim Cabot graduated from Columbia University with a BA degree in After working in the process chemical industry for 14 years, he founded Alacrity Material Technology which acquired the parent company of Sanford Process in
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