page 1/5 COLD SEALING PROCESS Proposal QUALITAL QUALANOD resolution: Meeting in June 2010, October 2011 Date of application: 1 January 2012 Parts of the Specifications concerned: Section 3.3.6 furthermore 2.3, 2.3.3, 3.3.1, 3.3.4, 3.4.3 and Appendix I Terminology (for information) Modified paragraph: 3.3.6 COLD SEALING PROCESS based on nickel salts and fluorinated salts (see following pages)
page 2/5 3.3.6 Cold sealing process based on nickel salts and fluorinated salts This section gives prescriptions for the implementation of "cold sealing" processes based on nickel salts and fluorinated salts (notes 1, 2 and 3). It incorporates the knowledge about these processes gained in the past years, and defines the most important parameters. The process is divided into 2 steps: in the first one the anodic coating is sealed, in the second one the anodic coating is hydrated. Anodizing conditions As for other sealing processes it is essential to produce a good quality anodic oxide film according to the conditions stipulated in section 3.3.4. Note 1 Cold sealing processes are based on chemicals which diffuse into the pores of the anodic oxide film and initiate a chemical reaction. It depends not only on the temperature but also on the chemicals used and other process factors. This specification relates only to cold sealing processes based on nickel fluoride. Note 2 The product available on the market can be a mixture of nickel salts and fluorides or fluorinated salts, where nickel fluoride can be only a minor part of the total amount. Note 3 Since the consumption of fluoride is slightly higher than the stoichiometric amount of nickel, some products on the market contain a slight excess of fluorides. A) First step of the sealing process 1) Concentration of the product: Nickel ion content 1.5 ± 0.3 g/l Free fluoride ions 0.50 ± 0.25 g/l 2) Bath temperature: 25 to 30 C 3) ph: 5.8 7.0 (preferably 6.5 ± 0.2) 4) Sealing time: 1.0 ± 0.2 min/µm of the anodic coating 5) Phosphate ions in the solution shall be less than 5 ppm Rinsing after cold sealing is essential and it is strongly recommended not to use demineralised water. Note 4 An excess of fluorides, especially in presence of a low ph produces a rapid degradation of the solution due to a chemical attack to the oxide surface. This attack is evident especially on polished or brightened parts. Note 5 An excess of ions different from nickel and fluoride can induce a reduction in the activity of the solution; in this case filtration can help to overcome the problem.
page 3/5 SUPPLEMENTARY REQUIREMENTS Chemical components The supplier should give the anodiser precise details of the percentage of active components and, if a powder, the percentage of insoluble matter in the products. Preparation of the bath The quality of the water shall be checked before use; it is advisable to use demineralised water to make up the bath. Operating parameters The operating parameters for cold sealing are critically important and shall be closely controlled to achieve a satisfactory result. It is also important to remember that the parameters are interdependent; for example, a high fluoride ion concentration requires a lower operating temperature and/or a shorter sealing time and a higher ph. Bath concentration The most important bath constituents are nickel and fluoride. An excess of free fluoride ions can damage the anodic coating. The nickel ion and free fluoride contents shall be maintained within the following levels: Nickel ion content 1.5 ± 0.3 g/l free fluoride ion content 0.50 ± 0.25 g/l In some cases, 5-10% of the nickel may be substituted by cobalt to minimize the greenish shade. The free fluoride and nickel content of the bath shall be checked at least once per shift and the bath replenished with extreme care, avoiding use of the bath until the substances added have been fully solubilised. Sometimes, nickel fluoride can contain insoluble matter. It is advisable to make additions in a mixing chamber outside the bath. Moreover, fluoride is consumed at a higher rate than nickel, and additions of ammonium or potassium fluoride will be required to maintain the correct balance. Analytical methods for checking the baths should be provided by the supplier. Generally an EDTA method is used for nickel and a potentiometric method with an ion-sensitive electrode for free fluoride. Note 6 It is advisable to avoid the use of hydrofluoric acid or too acidic fluorinated salts able to unbalance the ph of the solution. Strong variations of ph are never positive for the final quality. Bath temperature The bath shall be maintained at a temperature between 25 C and 30 C with a sensitive thermostatic device. This parameter has a great influence on the kinetics of the process. Too high a temperature, particularly when the free fluoride concentration is at a high level, causes damage to the anodic oxide film and results in a powdery surface.
page 4/5 Bath ph The ph of the solution shall be maintained between 5.8 7.0 (preferably 6.5 ± 0.2). Generally, the higher the ph the better, but it is not possible to go above 7.0 without causing a slight precipitation of nickel hydroxide. The ph affects the amount of nickel precipitated in the pores, and below 5.8 insufficient nickel is deposited, and a chemical attack on the anodic coating can be generated by fluoride. Note 7 The ph should be measured with utmost care as fluoride in the solution can attack the ph electrodes or damage the glass membrane. This makes it very important to check the ph electrodes at regular intervals. Sealing time The sealing time shall be 1.0 ± 0.2 min/µm of the anodic coating. Rinsing after cold sealing Thorough rinsing in cold tap water is essential after cold sealing. In fact demineralised water does not rinse properly and can contaminate the subsequent solution. B) Second step of the sealing process To complete the cold sealing process, the treated parts need to be exposed to high humidity for some time, which can be accelerated by dipping the cold sealed parts in a hot water bath. The bath shall contain either tap water and 4.0 ± 1.0 g/l nickel sulphate or nickel acetate, or demineralised water with an antismut additive, and shall be operated at a temperature of at least 60 C (preferably 70 C). The parts shall be immersed in the bath for 1.0 ± 0.2 min/µm. This treatment makes the work easier to handle and check, and shall be considered an essential part of the treatment. Thorough rinsing between cold sealing and the hot water treatment is absolutely essential as the fluoride ions can inhibit the conventional sealing processes. Cold sealed films are more prone to crazing than conventionally sealed films, especially when exposed in warm, dry environments. This effect is greatly reduced by the treatment in hot water after cold sealing. QUALITY CONTROL If the cold sealing process is applied as described, including immersion in hot water after cold sealing, the sealed work can be tested in the same way as conventionally sealed work. The most suitable tests are the dye spot test according to EN 12373-4 and the weight loss test according to EN 12373-7. The acceptance limits are those specified in sections 2.3.1 and 2.3.3.
page 5/5 2.3 Sealing and impregnation tests This section specifies the tests that shall be used to assess sealing quality and the associated criteria for acceptable performance. In cases where additives designed to prevent smutting are used in the sealing baths, special care should be exercised and greater attention paid to the referee test and the weight loss results and, where appropriate, the dye spot test. 2.3.3 Measurement of loss of mass after immersion in phosphoric acid/chromic acid solution with prior acid treatment according to EN 12373-7 (weight loss test) This test is the referee test to evaluate sealing quality. The maximum permissible loss of mass shall be 30.0 mg/dm². When a lot is to be inspected, the weight loss test shall always be performed on the part with the highest admittance or, if cold sealing impregnation is used, on the part with the highest thickness value. 3.3.1 Process requirements Sealing processes applying any principle other than hydrothermal sealing or cold sealing impregnation shall not be used unless they have been tested as stipulated in Appendix VI and approved by QUALANOD. 3.3.4 Anodizing This section indicates typical batch anodizing conditions with hydrothermal sealing or impregnation (cold sealing). Other electrolytes and/or other conditions may be used provided that the anodizing quality is at least as good as the quality produced by anodizing according to the Specifications. 3.4.3 Instruments and solutions for sealing tests The plant shall have at least one instrument for measuring admittance and a reference unit for checking the reading accuracy of the device. Exception: If a plant uses cold sealing impregnation only, this instrument is not necessary. App. I IMPREGNATION OR SO CALLED COLD SEALING OF ANODIZED ALUMINIUM A sealing treatment after anodizing consisting of impregnation based on nickel fluoride followed by ageing in a hot water treatment.