Innovative Cr-free anodizing & sealing processes for corrosion protection of aerospace aluminum alloys

M. Augros1*, A. Viola1, E. Sion1, C. Jablonski2, C. Metral2, V. Moutarlier3, M. P. Gigandet3, A. Gehin4, E. Rocca4, J. Steinmetz4, L. Arurault5
1

Messier-Bugatti (Safran group) Laboratoire matriaux & procds - 5 rue St Exupry 67129 Molsheim cedex (France) 2 Aircelle route du pont VIII 76700 Gonfreville l'Orcher (France) 3 ITSFC-LCMI - 16 route de Gray 25030 Besanon cedex (France) 4 LCSM UHP Nancy 1 - BP 239 54506 Vandoeuvre les Nancy cedex (France) 5 CIRIMAT-LCMIE universit Sabatier - 118 route de Narbonne 31062 Toulouse cedex 9 (France)

Abstract As a part of the "Proxy 3A" project (under French government foundings), the companies and research laboratories mentioned above work together on new environmentally-friendly anodizing and sealing processes in order to suppress organic coatings and to improve adhesion properties. For each process, substantial work is done in order to understand and explain the mechanisms used. Introduction The corrosion protection scheme on Messier-Bugatti aluminum parts consists of 3 steps : sulfuric acid anodizing (SAA), sealing in a nickel-acetates solution and double-layer water soluble organic coating, whereas Aircelle applies directly the adhesive on an adhesion primer (containing strontium chromates) after having performed a chromic acid anodizing. The objectives of this study are the following : - eliminate hexavalent chromium - improve paint adhesion properties - enhance corrosion resistance - avoid micro-cracks of sealed anodizing layers at high temperature (~100C) In this paper, anodizing studies are presented in the first part while the second part deals with sealing processes. Anodizing Influence of ramping on morphology of porosity, corrosion resistance and paint adhesion characteristics : In anodizing specifications, the ramping is not always specified. On 2214 alloy, 3 different ramping : 3, 6 and 15V/min are tested in order to study the influence on the anodizing layer morphology and its corrosion and adhesion properties. Figure 2 shows that the slower the voltage is applied during anodizing, the more homogeneous the surface morphology of the pores.

a. b. c. Figure 2 : Field-Emission Scanning Emission Microscope (FEG-SEM) surface observation on anodized AA2214 with different rampings a : 3V/min, b : 6V/min, c : 15V/min * corresponding author : myriam.augros@messier-bugatti.com SURFAIR 2006

Table 2 gives corrosion and paint adhesion results. We can notice that when the anodizing voltage is applied slowly (3V/min), corrosion resistance and paint adhesion properties are improved.
ramping thickness 800h salt spray1 paint adhesion2 3V/min 7.5 0 pit cl 3 2214 6V/min 7-8 1 pit cl 5 15V/min 7 5 pits cl 5 Table 2 : corrosion and adhesion results on 2214 anodized samples (SAA) with different rampings 1 neutral salt spray test in accordance with ISO 9227 2 adhesion test in accordance with ISO 2409 after 14 days immersion in deionized water at 20C on samples sealed in a nickel acetates solution and coated with chromium-free water-based paint and a low VOC polyurethane top coat alloy

Thickness of anodizing layers (SAA) influence on corrosion resistance : In order to study the influence of the thickness of anodic layers on corrosion resistance, it is necessary to form oxide layers with identical morphology and porosity. Therefore, during anodizing, we have to work with the same electrolyte, temperature and voltage. To obtain different thickness on our samples, we only adjust the anodizing duration. In this way, three AA2214 samples with the following oxide layer thickness : 2, 6 and 10m are prepared. The electrochemical behavior of each sample is evaluated, before and after sealing in boiling water, by anodic polarization tests in a sodium chloride solution (NaCl 50g/L 35C). As illustrated in figure 1, the results show that for unsealed samples as well as for sealed samples, the thicker the oxide layer (in the case of SAA), the higher the pitting potential. We have thus demonstrated that the thickness of the anodizing layer has a great influence on corrosion properties. A thick oxide layer is necessary to achieve a good corrosion resistance.
1

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0.6 2 !m essai 1 0.4 2 !m essai 2 6 !m essai 1 6 !m essai 2 0.2 10 !m essai 1 10 !m essai 2 0 -0.6

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0 E (V/ECS)

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Figure 1 : anodic polarization curves for 3 AA2214 anodized (SAA) and sealed (boiling water) samples

Thickness of anodizing layers influence on fatigue behavior : In the literature, it is commonly assumed that the thicker the anodic layer, the lower the fatigue resistance. In order to demonstrate that thickness is perhaps not the only parameter influent on fatigue behavior, various anodizing processes are tested on AA2214 and 7050. The anodizing processes used, thickness of anodic layers obtained and fatigue results are given in table 1. These results show that for 7050 alloy endurance limit is slightly higher after SAA than after CAA even though the SAA layer is 5 times thicker. This demonstrates that the electrolyte used for anodizing and thus the oxide layer morphology has a great influence on fatigue behavior.

average 107 cycles endurance limit2 (MPa) 0 275 CAA 2 268 2214 SAA 5-6 246 SCAA 5-6 258 0 300 7050 CAA 1-3 170 SAA 10-12 190 Table 1 : fatigue results for 2214 and 7050 alloys with different anodizing processes 1 CAA = chromic acid anodizing, SAA = sulfuric acid anodizing, SCAA = sulfuric-citric acid anodizing 2 endurance limit at 107 cycles determined by pulsed axial fatigue tests on double-radius test samples with a stress factor close to 1 alloy thickness (m)

anodizing process1

Anodic pulse anodizing : It is known that pulse anodizing creates a compact and thick oxide layer and that the pulsating process allows to decrease the process duration. That is why we have tested anodic pulse anodizing and voltage and time influence on growth of the oxide layer and on corrosion resistance. Figure 3 defines the electrical parameters of the anodic pulse SAA process tested.
voltage (V) E1

E2 0 T1 anodizing time (min) T2

Figure 3 : definition of the voltage applied during anodic pulse anodizing

After several experiments with different electrical parameters, the thickness and density of the oxide layers obtained are measured. The results depend on the aluminum alloys tested. For 2214 and 7050 alloys, with high voltage (E1 and E2) and short T2 time, the growth of the anodic layer is faster and the density of the aluminum oxide is higher than with constant voltage. Morphology of the oxide layers formed are observed using a FEG-SEM on AA1050 samples. The difference between constant voltage anodizing and anodic pulse anodizing is illustrated in figure 4. It reveals that with pulse anodizing, the pore diameter does not seem constant and that the pores are not columnar anymore but ramified.

a. b. Figure 4 : FEG-SEM observations of the structure of anodic layers on AA1050 (fractography) a : constant voltage SAA, b : anodic pulse SAA

Electrochemical tests in a sodium chloride electrolyte on samples having the same oxide layer thickness show that the pitting potential of pulse anodized samples can be higher than the one for constant voltage anodizing (see polarization curves in figure 5). Depending on the electrical parameters, using anodic pulse SAA allows to form corrosion-resistant oxide layers faster than "conventional" SAA.

1 0,9 0,8 0,7 0,6 0,5 0,4 0,3 0,2 0,1 0 -0,7

essai n16 essai n12

constant voltage anodizing essai n4

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Figure 5 : anodic polarization curves for constant voltage SAA and anodic pulse SAA on AA2214 samples (all samples tested have the same anodizing layer thickness)

Influence of mineral additives (on morphology and corrosion) : After CAA, all aluminum alloys exhibit outstanding corrosion properties because chromates act as corrosion inhibitors. Molybdate (MoO42-), cerium III and IV (Ce III and IV), tungstate (WO42-), vanadate (VO43-) and permanganate (MnO42-) have potentially the same corrosion inhibition properties as hexavalent chromium. So the influence of these ions is tested on 2214 alloy. For this, the ions are added to a sulfuric acid bath. Their influence on the growth of the oxide layer, on its composition and on its corrosion resistance is studied. The addition of such mineral compounds in a sulfuric acid bath leads to a slightly faster oxide layer growth except with MoO42- and Ce III. Global discharge optical emission spectroscopy (GDOES) analysis show that Mo, Mn and Ce are incorporated in the anodic layers formed with molybdate, permanganate and cerium IV respectively. As illustrated in figure 6, anodic polarization tests demonstrate that the corrosion resistance is improved with the addition of Ce IV, VO43- and MnO42-. Moreover, in the case of MoO42-, Ce IV and MnO42-, GDOES analysis are performed on corroded samples (cf. figure 7). We observe a decrease of these additives content after corrosion, which indicates that these additives react during the corrosion process.
1 0,9 0,8 0,7 OAS OAS + Mo OAS + Ce III OAS + Ce IV OAS + W OAS + V OAS + Mn

i (mA/cm?)

0,6 0,5 0,4 0,3 0,2 0,1 0 -0,7

E (V/ECS) -0,65 -0,6 -0,55 - 0,5 -0,45 -0,4 - 0,35 -0,3

Figure 6 : anodic polarization curves for SAA + additives

1600 1400 1200 1000
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Al S x100 O x4000 Cu x5 Ce x1000

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0 50 100 150 200 250 300 a. b. temps (s) Figure 7 : GDOES spectra of SAA + Ce IV before (a) and after (b) corrosion (immersion in a NaCl solution)

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Sulfo-tartaric acid anodizing role of tartaric acid For environmental concerns, industrials tend to use anodizing baths with lower content of acids. This is the reason why we have studied a "low concentration" sulfuric acid anodizing (DSAA). Moreover, as Boeing company has patented an anodizing bath composed of sulfuric and boric acids, a tartaric-sulfuric acid anodizing (TSAA) is studied in order to determinate whether tartaric acid plays a role in the anodizing process. The baths used are the following : - DSAA : 40g/L sulfuric acid at 37C - TSAA : 40g/L sulfuric acid + 80g/L tartaric acid at 37C On 2024 and 7175 alloys, tartaric acid has no influence on growth of the oxide layer and the surface porosity is the same for DSAA and TSAA. After boiling water sealing, the electrochemical behavior in a 50g/L sodium chloride solution at 35C is slightly better with the addition of tartaric acid in the anodizing bath (cf. polarization curves for 2214 alloy in figure 8) but there is no significant influence on salt spray results. To conclude, the addition of 80g/L tartaric acid in a 40g/L sulfuric acid bath at 37C does not seem to play a role on the main properties of the oxide layer formed.
1 DSAA N1 DSAA N2 TSAA N1 TSAA N2

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0 -0,5 -0,3 -0,1 0,1 0,3 0,5 E (V/ECS)

Figure 8 : anodic polarization curves for DSAA and TSAA (sealed with boiling water)

Sealing Study of water, potassium dichromate and nickel acetates sealing mechanisms : First of all, morphology of sealed anodizing layers is observed in fractography using a FEG-SEM. The porosity of the oxide layer does not seem filled but the surface morphology is different. As can be seen in figure 9, after boiling water sealing, we observe a thin layer on the surface and after potassium dichromate sealing, the smallest pores are not seen anymore (the pores seem thus partly filled).

a. b. c. d. Figure 9 : surface FEG-SEM micrographies on (a) unsealed sample, (b) boiling water, (c) K2 Cr2O7 and (d) nickel acetates sealed samples (7175 aluminum alloy)

Gravimetric thermal analysis (GTA) indicates that the decomposition temperature obtained before and after sealing is the same which demonstrates that there is no structural change during sealing (in the case of water, potassium dichromate or nickel acetates sealing). As illustrated in figure 10, we obtain the same curves for these 3 sealing solutions by GTA and differential thermal analysis (DTA). We also observe that, in the case of potassium dichromate sealing, chromium is found in the whole thickness of the oxide layer (but its content decreases from the surface to the interface). After nickel acetates sealing, nickel has been incorporated only in surface.

1050 colmat K2Cr2O7 1050 colmat H2O

1050 colmat anoseal

3
HF (!V)

0 0 -1 200 400 600 800 1000 1200

-2 Temprature (C)

Figure 10 : DTA curves for 3 conventional sealing solutions (water, K2 Cr2O7 and nickel acetates) on AA1050

In-situ electrochemical study of hydrothermal sealing : In order to monitor the sealing process, in-situ EIS measurements are performed in the sealing bath at 98C on anodized 7175 samples. We then determine the evolution of the pores resistance (Rp) with sealing time for several sealing solutions (cf. figure 11). We notice that for H2 O, K2 Cr2 O7 and nickel acetates sealing, there is a fast increase of the pores resistance (Rp) between 0 and 30min. From these results, we can conclude that the optimum sealing time is around 30min.
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Figure 11 : Rp value vs time for water, K2Cr2O7 and nickel acetates sealing

New hydrothermal solutions based on carboxylic acids or cerium salts : 2 new sealing solution types have been tested : carboxylic acids and cerium salts (nitrates, acetates and sulfates). These new sealing processes are characterized and the results are compared with those obtained with conventional (H2 O, K2Cr2O7 and nickel acetates) sealing. FEG-SEM investigations show that there is an organic layer on the surface (cf. figure 12), as it has been already seen in the case of nickel acetates sealing. When exposed to 120C, the samples sealed with carboxylic acids does not show any cracking whereas those sealed with cerium acetates have microcracks on their surface (although TGA analysis show that the oxide layers sealed with cerium acetates have a lower water content than with other conventional sealings). Corrosion resistance is evaluated on 7175, 7050 and 2214 samples after SAA and sealing (SST and EIS measurements). After salt spray test, a good corrosion resistance is achieved on 7175 alloy sealed with carboxylic acids and on all alloys tested when sealed with cerium acetates. The magnitude of the impedance (|Z|) measured for oxide layers sealed with carboxylic acid is quite high whereas |Z| is very low on samples sealed with cerium salts (cf. figure 13). It seems that anodizing layers sealed with cerium salts have the same electrochemical behavior as K2Cr2O7 (low impedance values but good performance in SST). Finally, paint adhesion properties of both sealing processes are tested. We obtain good results for cerium salts sealing but the adhesion results are quite bad on samples sealed with carboxylic acids.

a. b. Figure 12 : surface FEG-SEM observations on AA2214 samples sealed with (a) carboxylic acid and (b) cerium acetates
1,E+07
#2214 colmat Ce(CH3COO)3

1,E+06

#2214 colmat HC10

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1,E+00 1,E-03

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Figure 13 : EIS spectra (Bode representation) measured on 2214 + SAA + carboxylic acid or cerium acetates sealing

Sealing with cerium salts (influence of anion type and pH of the solution) : When sealing with various cerium salts, we obtain important differences in terms of corrosion resistance. But we do not know if this behavior is due to the anion type or the pH of the sealing solution. For this study, cerium acetates, cerium sulfates and cerium nitrates solutions are tested. From salt spray and EIS results in table 3, we can conclude that there is no clear influence of the pH of the cerium salt solution or that it is not the only influent parameter. There is a higher influence of the anion type.
sealing solution salt spray results EIS results nickel salt pH (after 500h) impedance at low f impedance at medium f 6.3 no pit low low Ce(CH3COO)3 4 some pits high low Ce(SO4)3 5 some pits low low 4 some pits medium high Ce(NO3)3 6.5 few pits medium high Table 3 : corrosion results on 2214 alloy treated by SAA and sealed with cerium salts (EIS = Electrochemical impedance spectroscopy performed in NaCl solution)

Metallic impregnation (zinc, nickel) : An other way to improve the corrosion resistance of aluminum alloys after anodizing is impregnation of metals at low temperature (usually 25C) and under an alternative voltage. Zinc and nickel impregnation are tested on 2214 and 7010 samples treated by SAA. Zinc or nickel sulfate solutions are used. For each process, influence of time and voltage is studied.

Zinc is incorporated only in surface of the oxide layer. The process tested leads to the same electrochemical behavior as an unsealed anodizing layer. Thus the corrosion resistance does not seem improved by zinc impregnation. After nickel impregnation, the corrosion properties seem better. Moreover we have demonstrated that nickel is incorporated in the whole thickness of the oxide layer, which is a very interesting characteristic. Conclusion and perspectives Various anodizing and sealing treatments have been tested in this study. The use of a slow ramping to apply the voltage during the anodizing process is also beneficial for corrosion resistance and adhesion properties. We have seen that it is necessary to form a anodizing layer with an optimized thickness to achieve a good corrosion resistance (knowing that this is not detrimental for fatigue resistance). Another good mean to obtain corrosion-resistant oxide layers is to use anodic pulse SAA. This is a process that can improve sealing of oxide layers and that can also enable to obtain better adhesion properties. It is also interesting to realize anodizing in a bath with a low concentration of sulfuric acid. Nevertheless, no influence of tartaric acid in the sulfo-tartaric anodizing process at 37C has been demonstrated. Several inorganic additives have also been tested in a sulfuric acid bath. Cerium IV, permanganate and vanadate are interesting in terms of corrosion resistance. The sealing mechanisms are not clearly understood yet. We have demonstrated that there is no chemical reaction or structural change in the semi-crystalline or amorphous oxide layer during the sealing process. In-situ EIS measurements (performed in the sealing bath at 98C) enables to monitor the sealing process and to determine the optimum sealing time. New sealing solutions have also been characterized : carboxylic acids and cerium salts. Cerium acetates sealing seems interesting in terms of behavior at high temperature (120C), corrosion resistance and paint adhesion properties. Finally, we have studied metallic impregnation of zinc and nickel. Zinc impregnation does not lead to an improvement of corrosion properties, while nickel impregnation seems more interesting because nickel has been incorporated in the whole thickness of the oxide layer. Many environmentally-friendly high-performant processes for corrosion protection of aluminum alloys are presented in this paper. It would now be interesting to associate some of them in order to get the best corrosion protection on aeronautical aluminum alloys.