Metal treatment – Process of modifying or maintaining internal physical... – Processes of coating utilizing a reactive composition which...
Reexamination Certificate
1996-07-19
2002-08-27
Kastler, Scott (Department: 1742)
Metal treatment
Process of modifying or maintaining internal physical...
Processes of coating utilizing a reactive composition which...
C148S253000
Reexamination Certificate
active
06440231
ABSTRACT:
This invention relates to a process for the pretreatment of metal surfaces before bonding to rubber, by which both steel, galvanized steel and also aluminum and magnesium can be treated individually or in combination with one another. The process does not require any solvents and does not involve the use of chromium compounds either in the process itself or in any post-rinse steps.
The process is particularly suitable for producing rubber-to-metal bonds where the unvulcanized rubber mastic is applied to the metal and is vulcanized in contact with the metal surface, generally using vulcanization aids.
DISCUSSION OF RELATED ART
Before the rubber-to-metal bond is established, the metal surfaces have to be cleaned and then brought into a state suitable for adequate adhesion. Blasting processes, for example, are suitable for this purpose. Unfortunately, they are attended by the disadvantage that, in many cases, the corrosion resistance of the rubber-to-metal bond is inadequate. In addition, the blasted parts require rapid further treatment. The considerable waste which accumulates during blasting leads to disposal problems. Accordingly, it is standard practice to subject the metal surfaces to a chemical pretreatment which reduces their susceptibility to corrosion and, at the same time, improves the ability of the rubber to adhere to the metal.
A review of standard chemical pretreatment processes can be found in the article by S. Lizumi (“Durability of Rubber-Metal Bonds in Corrosive Environments”, Int. Polym. Sci. Technol. 19 (9), T/19-T/28 (1992)). Zinc or iron phosphating are mentioned as chemical pretreatment processes for iron-containing materials while yellow or green chromating is mentioned for aluminum. There is no reference to a process which is suitable both for aluminum and for steel. The chromating of aluminum and the zinc or iron phosphating of steel are widely used methods for pretreating the metal surfaces which are used not only to establish rubber-to-metal bonds, but also to a far larger extent as a pretreatment before painting.
The corrosion-inhibiting properties of a phosphate coating are generally further improved by a passivating after-rinse, often with chromium-containing solutions. For example, DE-A-26 38 723 describes a process for improving the hydrolysis resistance of the bond between a steel alloy and rubber products which comprises inter alia the steps of applying a crystalline zinc phosphate coating and post-rinsing of the zinc phosphate coating with a solution of chromic acid.
The problem addressed in U.S. Pat. No. 5,143,562 was to provide a corrosion-inhibiting treatment process by which different metal surfaces, for example steel and aluminum, could be treated at the same time. This process is based on iron phosphating and uses aqueous solutions which may contain the following components: phosphate ions, complex and simple fluorides, iron complexing agents, hydroxylamine as a phosphating accelerator, oxidizing agents, for example aromatic nitro compounds or molybdates, surfactants, foam inhibitors and also hydrotropes for improving the solubility of these components. According to the statement of problem, this process is used to obtain permanent protection of the metal surface against corrosion and, more particularly, as a pretreatment before subsequent painting. There is nothing to indicate whether the process is suitable for the production of rubber-to-metal bonds.
Testing of the suitability of pretreatment processes for the production of rubber-to-metal bonds requires methods by which the strength of the bonds can be determined, particularly after exposure to corrosive influences. A summary of such methods can be found, for example, in the article by D. Beiersdorf and H. Scheer entitled“WäBrige Gummi-Metall-Haftmittel als Alternative zu lösemittelhaltigen Systemen (Water-Based Rubber-Metal Adhesives as an Alternative to Solvent-Containing Systems)”, Kaut-schuk+Gummi Kunstst 44 (7), 674-678 (1991). For example, the methods known to the expert as standard tests for tensile shear strength, peel strength and resistance to boiling water are explained in this literature reference.
The problem addressed by the present invention was to provide a process which would improve the strength and corrosion resistance of rubber-to-metal bonds and which could be applied to steel, galvanized steel, aluminum and magnesium either individually or in combination with one another.
SUMMARY OF THE INVENTION
The problem stated above has been solved by a process for the production of a rubber-to-metal bond on steel, galvanized steel, aluminum and/or magnesium, comprising at least the following steps:
a) chemical pretreatment of the metal parts,
b) intermediate rinsing,
c) vulcanizing-on of natural or synthetic rubber using primers and/or binders,
characterized in that the chemical pretreatment in step a) is carried out with an aqueous solution with a pH value of 3.5 to 5.5 which contains
4 to 20 g/l of phosphate ions,
0.1 to 1 g/l of free or complexed fluoride and
0.04 to 1 g/l of nitrate ions.
DETAILED DESCRIPTION OF THE INVENTION
The anions mentioned may be used in the form of the free acids or in the form of water-soluble salts. Suitable water-soluble salts are the alkali metal and ammonium salts, preferably sodium salts. The pH value has to be increased or reduced to the range according to the invention, depending on whether the anions are used as acids or as salts. If it has to be increased, the pH value is preferably adjusted with alkali metal hydroxide, more especially sodium hydroxide. If it has to be reduced, the pH value is preferably adjusted with an acid which forms the anions mentioned, more especially phosphoric acid. Under the pH conditions and at the concentrations according to the invention, the phosphate ions are mainly present in the form of the dihydrogen phosphate ions and the monohydrogen phosphate ions.
The necessary fluoride may be present in free or in complexed form. Fluoride contents in the upper concentration range are advisable when the baths have built up an aluminum content of 3 to 10 ppm through erosion. Higher Al contents lead to a reduction in the performance of the treatment baths. The freed flouride source is selected in particular from hydrofluoric acid, ammonium fluoride and alkali metal fluorides. Complex fluoride may advantageously be used in the form of the fluorocomplexes of silicon, titanium and zirconium. It is particularly preferred to use potassium hexafluorotitanate. The bath solution may also contain free and complexed fluoride alongside one another providing the total fluoride concentration does not exceed 1 g/l. Higher fluoride contents adversely affect layer formation on Al.
The corrosion prevention and adhesion values obtainable by pretreatment of the metal parts in accordance with the invention can be further improved by adding molybdate ions to the treatment solution in quantities of 0.05 to 0.5 g/l. Ammonium and alkaline earth metal molybdates are particularly suitable sources for these ions, sodium molybdate preferably being used.
In order to improve the wetting of the metal parts with the pretreatment solution, it is advisable to add nonionic surfactants to the solution in quantities of 0.5 to 2 g/l. The nonionic surfactants are preferably selected from the group of ethoxylation and/or ethoxylation/propoxylation products of fatty alcohols containing 10 to 18 carbon atoms. Suitable examples of such nonionic surfactants are adducts of 6 moles of ethylene oxide and 8 moles of propylene oxide with a fatty alcohol containing 10 to 12 carbon atoms, adducts of 5 moles of ethylene oxide and 4 moles of propylene oxide with a fatty alcohol containing 12 to 14 carbon atoms and adducts of 8 moles of ethylene oxide with fatty alcohols containing 12 to 15 carbon atoms. For application by spraying where excessive foaming of the treatment solution has to be prevented, it is advisable at least partly to use those nonionic surfactants which are end-capped, i.e. which are present as ethers. One example of such nonionic surfactants
Beiersdorf Wolf-Dieter
Foell Juergen
Gies Birgit
Gruber Werner
Kuhm Peter
Harper Stephen D.
Henkel Kommanditgesellschaft auf Aktien
Kastler Scott
Ortiz Daniel S.
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