WO1992014862A2 - Procede de traitement des surfaces contenant de l'aluminium - Google Patents

Procede de traitement des surfaces contenant de l'aluminium

Info

Publication number
WO1992014862A2
WO1992014862A2 PCT/US1991/009668 US9109668W WO9214862A2 WO 1992014862 A2 WO1992014862 A2 WO 1992014862A2 US 9109668 W US9109668 W US 9109668W WO 9214862 A2 WO9214862 A2 WO 9214862A2
Authority
WO
WIPO (PCT)
Prior art keywords
aluminum
primary film
process according
film
phosphate
Prior art date
Application number
PCT/US1991/009668
Other languages
English (en)
Other versions
WO1992014862A3 (fr
WO1992014862A1 (fr
Inventor
Yasunobu Matsushima
Shigeo Tanaka
Daijiro Tani
Original Assignee
Henkel Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP40544690A external-priority patent/JPH04224684A/ja
Application filed by Henkel Corporation filed Critical Henkel Corporation
Priority to BR9107278A priority Critical patent/BR9107278A/pt
Priority to AU91713/91A priority patent/AU655622B2/en
Priority to EP92903444A priority patent/EP0679200A1/fr
Publication of WO1992014862A1 publication Critical patent/WO1992014862A1/fr
Publication of WO1992014862A2 publication Critical patent/WO1992014862A2/fr
Publication of WO1992014862A3 publication Critical patent/WO1992014862A3/fr

Links

Definitions

  • This invention concerns a method of treating a surface including metallic aluminum or an aluminum alloy that is at least 45 % by weight, or preferably at least 85 % by weight, aluminum, in order to form on the surface a film which has excellent corrosion resistance, painting proper ⁇ ties and electrodeposition painting properties.
  • aluminum is to be understood as including aluminum alloys as specified above, and constitutions specified in percent ⁇ ages are to be understood as percentages by weight unless otherwise stated.
  • the process according to the invention is particularly suited to surfaces in sheet or strip form. In recent years, there has been a tendency to use aluminum sheet for parts of an automobile body in order to reduce the weight of automobiles.
  • the aluminum sheet or press formed aluminum sheet forms a com ⁇ posite material in which it is joined by welding, bonding or bolting to zinc alloy plated steel sheet, alloyed zinc plated steel sheet, zinc plated steel sheet, or the like.
  • This present invention also concerns a method of forming films which have excellent corrosion resistance and paint ⁇ ing properties on these composite materials.
  • phosphate treatment liquids which con ⁇ tained fluoride, especially in the form of silicofluoride, were used in the main for forming phosphate films on alum ⁇ inum sheets and formed and worked aluminum sheets.
  • Acidic sodium fluoride and acidic potassium fluoride have been added to phosphate treatment liquids as a means of precipitating and removing the Al 3+ ion as K 2 NaAlF 6 com ⁇ pounds in order to prevent the lowering of the forming properties due to the admixture of Al 3+ ions as mentioned above, but fluorine is contained in the precipitate and this is undesirable from the viewpoint of pollution.
  • This present invention takes as one of its objects the provision of a method for the formation of phosphate films with which the Al 3+ ion does not substantially increase in the phosphate treatment liquid and with which there is no deterioration of the phosphate film forming properties.
  • this present invention discloses a method for the uniform formation of a phosphate film which has ex ⁇ cellent corrosion resistance and painting properties on composite materials in which a press worked aluminum sheet and a steel sheet or a zinc based plated steel sheet are combined.
  • a primary film of Ni, Fe or Co, or a composite of two or more of these is formed on the aluminum sheet and washed with water.
  • Pure aluminum and aluminum alloys of which aluminum is the principal component for example pure aluminum such as IS and 2S, corrosion resistant aluminum and magnesium based alloys such as 52S and 56S, aluminum and manganese based alloys such as 3S, aluminum and magnesium alloys such as 61S and 63S, duralumin such as 14S, 17S and 24S, and extra super duralumin such as 74S and 75S can be used for the aluminum sheet in this present invention.
  • sheets of these aluminum materials are included among the aluminum sheets of this present invention.
  • a primary film of Ni, Fe, Co is formed on these aluminum sheets.
  • This primary film is obtained by coating Ni, Fe, Co on the aluminum sheet, preferably in an amount calculated as metal of 5 - 100 mg/m 2 using a non-electrolytic or cathodic electrolytic method.
  • This primary film can be formed using a simple method, as described hereinafter, and moreover it is not lost on cold forming and working or in the phosphate forming treatment and so it is desirable as a primary film.
  • An example of a method of forming a primary film of Ni, Fe, Co or a compositie non-electrolytically is de ⁇ scribed below.
  • First of all the aluminum sheet is de- greased and washed, using alkali for example.
  • the aluminum sheet is immersed for from 5 seconds to 2 minutes in a warm solution of 15 g/1 of sodium carbonate, 25 g/1 of sodium phosphate and surfactant, the oil and grease and the oxide film are removed from the aluminum sheet and a surface which is suitable for the deposition of Ni, Fe, Co or a combination thereof is obtained.
  • the de- greased and washed aluminum film is washed with water, neu ⁇ tralized with nitric acid, sulfuric acid or the like and washed with water.
  • the treatment liquid for forming the primary film is an aqueous solution, used at a temperature in the range from normal ambient temperature to 80° C, which contains Fe 2+ , Fe 3+ , Ni 2+ , and/or Co 2+ , and, by immersing the degreased and washed aluminum sheet in this - A - aqueous solution, or by spraying the aqueous solution onto the aluminum sheet, a primary film of Ni, Fe, and/or Co can be formed on the aluminum sheet.
  • the aluminum sheet is im ⁇ mersed in an aqueous solution which contains Fe 2+ , Fe 3+ , Ni 2+ , and/or Co 2+ and a thin film is formed on the aluminum sheet, for example by cathode electrolysis at a current density of 0.3 - 30 amps/dm 2 with a quantity of electricity of from 0.3 to 10 coulombs/dm 2 .
  • a solution in which from 20 to 50 grams of iron chloride or nickel chlor ⁇ ide or cobalt chloride and 100 milliliters ("ml") of in ⁇ dustrial hydrochloric acid have been dissolved in 1 liter of water can be used for the aqueous solution which con- tains Fe 2+ , Fe 3+ , Ni 2+ , and/or Co .
  • nitrates, sulfates, phosphates and condensed phosphates are suitable, non-exclusive counterions for the aforementioned metal ions, and phosphoric acid, sulfuric acid, and nitric acid are suitable, non-exclusive acids for ajusting the acidity of the plating solution.
  • the immersion time or cathode electrolysis time in the treatment liquid with which the primary film is formed is selected appropriately according to the composition of the aluminum sheet, but a metal primary film of Ni, Fe, and/or Co of some 5 - 100 mg/m 2 is formed on the aluminum sheet by means of this procedure.
  • the aluminum sheet is then washed with water and rinsed, whereupon an aluminum sheet on which a primary film of Ni, Fe or Co, or an alloy of two or more of these, is obtained as part of this present invention.
  • a phosphate film is then formed on the aluminum sheet on which the primary film has been formed, using a treat ⁇ ment liquid which contains fluoride.
  • the primary film when a phosphate film is formed on an aluminum sheet on which the primary film had been formed, the increase in Al 3+ ion in the treatment liquid is prevented and excellent phosphate film forming properties can be maintained over a long per ⁇ iod of time. Furthermore, after the primary film has been formed on the aluminum sheet, the secondary phosphate film has been formed and an anti-rusting oil has been applied, the product can be obtained as a surface treated aluminum sheet. Furthermore, the primary film is not lost even if the aluminum sheet is press formed using the usual press lubricating oils, and it is retained on the aluminum sheet surface after press forming.
  • composite mater- ials comprised of aluminum sheets and zinc plated steel sheets or plain steel sheets using aluminum sheets on which a primary film of Ni, Fe, and/or Co had been formed in an amount calculated as metal of 5 - 100 mg/m 2 , or an aluminum sheet obtained by press forming such a sheet, by joining with spot welding to the zinc based plated steel sheet or steel sheet.
  • a phosphate film was formed on these compos ⁇ ite materials using a phosphate film treatment liquid which contained fluorides of sodium and potassium, and good phos ⁇ phate films could be formed on the aluminum sheet and on the zinc plated steel sheet or steel sheet.
  • Figure 1 is a drawing which shows the shape and size of the pressed formed product in Examples 2, and Figure 2 is an explanatory drawing of the bonded composite work- pieces in example 3. Details of Some Preferred Embodiments of the Invention
  • the inventors prepared in each case 100 aluminum sheets on which a primary film had been formed as shown in Table 1, using commercially pure aluminum sheet (Type 2S)
  • Test panels were initially degreased and cleaned by immersion for 5 minutes in a solution of FINECLEANERTM 315, comemrcially available from Nihon Parkerizing Co. , Ltd. , at a temperature of 55 - 60 ° C. Panels were then treated with 1 % aqueous hydrochloric acid solution as a neutral ⁇ izing rinse before the treatments detailed above. with width of 300 mm, length of 300 mm, and thickness of 0.8 mm. These sheets were then subjected to the following process steps: De-grease and wash ⁇ water wash ⁇ neutral ⁇ ization rinse ⁇ water wash ⁇ primary film formation ⁇ wash ⁇ dry ⁇ anti-rusting oil coating ⁇ left to stand for 1 week indoors.
  • the de-greasing washing, neutralization and primary film forming treatment conditions were as shown in table 1.
  • the sa - pies were phosphated.
  • the phosphate film formation results are shown in Table 3.
  • the samples were also subjected to a Filiform Corro ⁇ sion Promotion Test Method, as follows: A specimen in which scratches had been made in a cationically electrode- posited paint film surface were immersed for 2 hours in 0.5N HC1 aqueous solution which contained 1% H 2 0 2 at 30°C and then washed with water and dried. Then, they were left to stand for 240 hours in a room at 40°C and 85% relative humidity, and an assessment was made after six of these cycles. The filiform corrosion length was less than 5 mm for Experiments 1. 1 and 1.4, 5 - 10 mm for the remaining Experiments 1.2, 1.3, 1.5, and 1.6, and more than 11 mm for Comparison Experiment 1.7.
  • the aluminum ion concentrations are given in parts per million by weight.
  • Degreasing Washing Immersed for 2.0 minutes in an aqueous solution of FINECLEANER L4460 (made by Nihon Parkerizing Co.) Furthermore, the press forming was carried out with deep cylindrical pressing as shown in figure 1. Also, the phosphate film forming treatment was carried out with the same immersion time (2.0 minutes/ sheet) using the same treatment liquid as in table 2. The results of phosphate film formation were as shown in Table 4. As shown in Table 4, the aluminum sheets on which a primary film of this invention had been formed and which had been press formed were such that a phosphate film could be formed in roughly the same way as with aluminum sheets which had not been subjected to press forming, as described in Table 3.
  • Seams were formed by spot welding formed hot dip gal ⁇ vanized steel sheets which had been press formed and worked, instead of the cold rolled steel sheet as noted in the preceding paragraph, onto aluminum sheet on which a primary film had been formed and a phosphate film forming treatment was carried out using the same procedure, and in this case again a good phosphate film was formed on the zinc plated steel sheet and the aluminum sheet.
  • a phosphate film which has excellent corrosion resistance and painting properties is formed uniformly, in a state in which the dissolution of aluminum into the phos ⁇ phate treatment liquid is suppressed, on an aluminum sur ⁇ face or a composite in which an aluminum surface, which may be press worked, is combined with a steel or a galvanized steel surface, which may or may not have been press worked.

Abstract

Un film primaire de Ni, Fe, et/ou Co est constitué sur une surface d'aluminium, un film phosphate est ensuite constitué sur cette surface d'aluminium ayant reçu ce film primaire, ou sur une surface d'un composite d'aluminium sur laquelle un film primaire a été constitué, avant d'être combiné à une tôle d'acier enduite à base de zinc. Cette méthode de traitement de surface n'entraîne pas les problèmes de pollution courants par l'ion Cr6+ et par F-, et l'on constate à l'usage une faible dégradation du liquide de traitement servant à réaliser le film phosphate.
PCT/US1991/009668 1990-12-25 1991-12-26 Procede de traitement des surfaces contenant de l'aluminium WO1992014862A2 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
BR9107278A BR9107278A (pt) 1990-12-25 1991-12-26 Processo para revistimento protetor de uma superfície metálica
AU91713/91A AU655622B2 (en) 1990-12-25 1991-12-26 Method for treating aluminum containing surfaces
EP92903444A EP0679200A1 (fr) 1990-12-25 1991-12-26 Procede de traitement des surfaces contenant de l'aluminium

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2/405446 1990-12-25
JP40544690A JPH04224684A (ja) 1990-12-25 1990-12-25 アルミニウム板およびその複合物の表面処理法

Publications (3)

Publication Number Publication Date
WO1992014862A1 WO1992014862A1 (fr) 1992-09-03
WO1992014862A2 true WO1992014862A2 (fr) 1992-09-03
WO1992014862A3 WO1992014862A3 (fr) 2004-04-29

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