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Passivation of Aluminum and Aluminum Alloys

aluminium passivation
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Tony

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Aluminum Passivation

Passivation of Aluminum and Aluminum Alloys

Abstract: For aluminum and aluminum alloy workpieces, whether obtained through chemical oxidation or anodization, the resulting oxide film is porous, prone to contamination, and has poor corrosion resistance. Even after coloration of the film, passivation and sealing treatment should be performed to enhance its corrosion resistance.

Passivation of Aluminum and Aluminum Alloys After Chemical Oxidation
Passivation treatment of aluminum and aluminum alloy workpieces with chemical oxide film is outlined in Table 1.

Table 1: Formulation and Process Conditions of Passivation Solution for Aluminum and Aluminum Alloys after Chemical Oxidation
Formulation No.Solution ComponentsContent /g.L-1Temperature /℃Time Baking TemperatureRemark
1Potassium dichromate(K3Cr4O7)30~5090~955~10min≤90Suitable for acid oxidation
2Chromium oxide(CrO4)20Room temperature5~15s≤50Suitable for alkaline oxidation
Passivation of Aluminum and Aluminum Alloys After Anodization Passivation treatment of aluminum and aluminum alloy workpieces after anodization is outlined in Table 2.
Table 2: Formulation and Process Conditions of Passivation Solution for Aluminum and Aluminum Alloys after Anodization
Formulation No./Solution composition and process conditions 12
Potassium dichromate(K3Cr4O7)
Potassium chromate(K2CrO4)
Temperature/℃
Time/min
40~70
80~95
10~20
50
80
20
Passivation Seal Treatment for Aluminum and Aluminum Alloy Oxide Films

Hot Water Sealing

(1) Principle

The Al2O3 on the surface and pore walls of the oxide film undergoes a hydration reaction in hot water (temperature greater than 80℃), producing hydrated alumina and causing the oxide film to expand (expansion rate of 33% to 100%). The expansion of the film reduces the pore size and ultimately seals it. The reaction can be represented as:

Al2O3 + H2O → 2AlO(OH) → Al2O3 •H2O

Distilled or deionized water is used for hot water, and tap water is avoided because it can lead to scaling in the pores, decreasing the transparency of the film. Ions such as Cl-, SO42+, PO43-, and Cu2+ in tap water can also hinder the sealing process due to pore blockage.

(2) Process

Temperature: 95 to 100℃.
pH Value: 5.5 to 6 (adjusted with acetic acid).
Time: 10 to 30 minutes.

Steam Sealing

(1) Principle

 Similar to hot water sealing.

(2) Characteristics

Faster sealing, unaffected by pH value, and higher corrosion resistance of the film. When sealing colored pores, dye loss is less compared to hot water sealing. However, disadvantages include higher pressure vessel costs, limitations in continuous operation for large workpieces, risk of film rupture during sealing of thick oxide layers, and higher costs.

(3) Process

Temperature: 100 to 110℃.
Pressure: 0.05 to 0.1 MPa.
Time (per film thickness): 4 to 5 minutes per micrometer.

Metal Salt Sealing

Immersing the anodized oxide film in a solution of metal salts for sealing is known as metal salt sealing. The metal salts used include acetates, nitrates, and sulfates of iron, zinc, copper, aluminum, etc. The mechanism involves the hydrolysis of metal salt solution within the micro-pores of the anodized oxide film, resulting in the formation of hydroxide precipitates that seal the pores. Two common methods are chromic acid sealing and hydrolysis salt sealing.

(1) Chromic Acid Sealing

Principle

In a solution of chromic acid salts, a chemical reaction occurs after the adsorption of chromic acid salts, leading to the formation of basic aluminum chromate [Al(OH)CrO4] and chromic aluminum [Al(OH)Cr2O7]. These compounds fill the pores of the film, achieving the sealing effect.

Table 3: Solution Formulation and Process Conditions

Table 3: Formulation and Process Conditions of Dichromate Sealing Solution
ItemsFormula
123
Potassium dichromate /g.L-1
Sodium carbonate /g.L-1
Sodium hydroxide /g.L-1
PH Value
Temperature/℃
Time/min
100
18
(or 3)
6~7
90~95
2~5
40~55
6.5~7
90~95
20~30
15
4
3
6.5~7.5
90~95
2~5

Several Points to Note

a. Prior to the sealing treatment, it is essential to thoroughly clean the workpieces to prevent any acid from being introduced into the sealing tank. Additionally, contact between the workpieces and the tank should be avoided to prevent damage to the oxide film.

b. Impurities in the sealing solution should be controlled. When SO42+ > 0.2g/L, a suitable amount of calcium chromate (CaCrO4) precipitate can be added and filtered out, otherwise, it could lead to lightening and whitening of the sealed workpieces. When SO42+ > 0.02g/L, potassium aluminum sulfate (K2Al2(SO4)4•24H2O) can be added at 0.1~0.15g/L to prevent whitening of the sealed workpieces and a decrease in corrosion resistance. When Cl- > 1.5g/L, the sealing solution needs to be diluted or replaced; otherwise, it can cause corrosion of the oxide film on the workpieces.

(2)Salt Hydrolysis Sealing

Principle

The process utilizes the hydrolysis of metal salts adsorbed by the oxide film, resulting in the formation of hydroxide precipitates that fill the pores and achieve the sealing purpose. Commonly used metal salts include cobalt and nickel salts, with the reaction equation as follows:
NiSO4 + 2H2O → Ni(OH)2↓ + H2SO4
The pore-sealing process is as follows:

a. The product of the hydration process (transparent substance) seals the pores.

b. Water is added for decomposition, leading to the precipitation of hydroxides within the micropores.

c. These precipitates chemically react with dye molecules to form metal-chromium complexes.

Formulation and Process Conditions of Salt Hydrolysis Sealing Solution can be found in Table

Table 4: Salt Hydrolysis Sealing Solution
No.FormulaProcess conditions
ElementContent/g.L-1PH ValueTemp/℃Time/min
1Nickel sulfate(NiSO4.7H2O)4.24.5~5.580~8510~20
Cobaltous sulfate(CoSO4.7H2O)0.7
Sodium acetate(CH3COONa.3H2O)4.8
Boric acid(H3BO3)5.3
2Sodium acetate(CH3COONa.3H2O)5.54.5~5.580~8510~15
Cobaltous acetate (CH3COO)2Co.4H2O)0.1
Boric acid(H3BO3)3.5
3Nickel acetate (CH3COO)2Ni.4H2O)5.55.5Boiling point30
Cobaltous acetate (CH3COO)2Co.4H2O)1.0
Boric acid(H3BO3)8

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Passivation of Aluminum and Aluminum Alloys

For aluminum and aluminum alloy workpieces, whether obtained through chemical oxidation or anodization, the resulting oxide film is porous, prone to contamination, and has poor corrosion resistance. Even after coloration