EP3350357A1 - Prétraitement de surfaces en aluminium avec des compositions contenant du zircon et du molybdène - Google Patents

Prétraitement de surfaces en aluminium avec des compositions contenant du zircon et du molybdène

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Publication number
EP3350357A1
EP3350357A1 EP16770231.5A EP16770231A EP3350357A1 EP 3350357 A1 EP3350357 A1 EP 3350357A1 EP 16770231 A EP16770231 A EP 16770231A EP 3350357 A1 EP3350357 A1 EP 3350357A1
Authority
EP
European Patent Office
Prior art keywords
workpieces
solution
metal
aqueous
aluminum
Prior art date
Legal status (The legal status 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 status listed.)
Granted
Application number
EP16770231.5A
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German (de)
English (en)
Other versions
EP3350357B1 (fr
Inventor
Norbert Maurus
Thomas Wendel
Nawel Souad Khelfallah
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chemetall GmbH
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Chemetall GmbH
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Publication date
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Publication of EP3350357A1 publication Critical patent/EP3350357A1/fr
Application granted granted Critical
Publication of EP3350357B1 publication Critical patent/EP3350357B1/fr
Active legal-status Critical Current
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
    • C23C22/44—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • C23C22/76—Applying the liquid by spraying
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/78—Pretreatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/78—Pretreatment of the material to be coated
    • C23C22/80—Pretreatment of the material to be coated with solutions containing titanium or zirconium compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/82—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/12—Light metals
    • C23G1/125—Light metals aluminium

Definitions

  • the invention relates to a method for the pretreatment of workpieces with a surface made of aluminum or aluminum alloys for non-cutting forming and / or joining by welding or gluing with similarly pretreated or otherwise otherwise precoated workpieces or with optionally pretreated parts made of steel and / or galvanized and / or alloy-galvanized steel, and for subsequent corrosion-protective treatment by phosphating, by chromium-free conversion treatment, by primer application or by painting.
  • the method of EP-B-700 452 envisages contacting surfaces of aluminum or its alloys with an aqueous solution prior to a second permanent anticorrosion treatment for pretreatment, comprising complex fluorides of the elements boron, Contain silicon, titanium, zirconium or hafnium individually or in admixture with each other in concentrations of the fluoro-anions of 100 to 4000 mg / l and have a pH of 0.3 to 3.5.
  • the parts made of aluminum or its alloys are subjected to a chipless and / or cutting deformation process, and / or connected to one another or to parts made of steel and / or galvanized and / or alloy-galvanized steel by gluing and / or welding.
  • the application of the optionally polymers containing certain state of the art solution can be done by spraying, dipping or no-rinse method, wherein in the case of the no-rinse method, the wet film amount between 2 to 10, preferably between 4 and 6 ml / m 2 metal surface should. Regardless of the form of application of the solution, it is advantageous to dry at temperatures between 40 and 85 ° C.
  • the parts made of aluminum or its alloys are acid or alkaline cleaned prior to the first conversion treatment, and cleaning steps and intermediate rinses with water and / or activating rinsing baths preferably take place before the permanent corrosion-protective treatment.
  • the object of the invention is a method for the pretreatment of workpieces with a surface made of aluminum or aluminum alloys for non-cutting forming and / or joining by welding or gluing, in particular for bonding by gluing, with similarly pretreated or otherwise otherwise precoated workpieces or with Parts made of steel and / or galvanized and / or alloy galvanized steel, in particular with similarly pretreated workpieces, and to provide a permanent corrosion protection treatment by phosphating and / or by a chrome-free conversion treatment and by primer application and / or painting, in particular by phosphating and a Chrome-free conversion treatment as well as varnishing, which regularly leads to workpieces with a sufficiently low volume resistance and at the same time good phosphatability and adhesive adhesion.
  • the method according to the invention should moreover lead to good temporary corrosion protection values and be largely insensitive to bath contamination by aluminum ions.
  • the object is achieved, on the one hand, by configuring the method according to the invention in such a way that the workpieces a) are immersed in a dipping or spraying with a mineral acid-containing aqueous, acidic solution,
  • aqueous, acidic solution which is chromium-free and contains Zr as complex fluoride and Mo as molybdate in a weight ratio (calculated as Zr / Mo metal) of Zr: Mo of 15: 1 to 3.5: 1, brought by dipping or spraying application in contact, so that after the subsequent drying a coating weight of 2 to 15 mg / m 2 of Zr and Mo results, the Solution contains 100 to 800 mg / l Zr and 30 to 100 mg / l Mo (calculated as Zr / Mo metal) and has a pH of 2.5 to 4.5.
  • the aqueous, acidic solution in step c) preferably contains Zr and Mo in a weight ratio of 15: 1 to 5: 1, more preferably from 13: 1 to 7: 1 and very particularly preferably from 1: 1 by immersion or spraying : 1 to 9: 1.
  • a coating weight of 2 to 12 mg / m 2 , particularly preferably 2 to 10 mg / m 2 and very particularly preferably 2 to 8 mg / m 2 of Zr and Mo preferably results in the case of immersion or spray application ,
  • the aqueous solution contains 250 to 700 mg / l Zr and 30 to 80 mg / l Mo, more preferably 400 to 600 mg / l Zr and 40 to 60 mg / l Mo and most preferably 475 in the case of immersion or spray application to 525 mg / l Zr and 45 to 55 mg / l Mo.
  • the aqueous solution in the case of immersion or spray application preferably has a pH of from 3.1 to 4.3 and more preferably from 3.6 to 4.0 and preferably a temperature of from 20 to 50 ° C. and more preferably from 20 to 30 ° C on.
  • the object is achieved by the method of the type mentioned according to the invention is designed such that the workpieces a) with a mineral acid-containing aqueous, acidic solution in the dipping or spraying,
  • roller coating method brings into contact, so that after the subsequent drying, a coating weight of 2 to 15 mg / m 2 of Zr and Mo results, the solution 0.4 to 7.5 g / l Zr and 0.4 to 7.5 contains g / l Mo (calc. as Zr / Mo metal) and has a pH of 1.0 to 3.0.
  • the aqueous solution when applied by roller coating 1, 0 to 6.0 g / l Zr and 1, 0 to 6.0 g / l Mo, more preferably 2.0 to 4.0 g / l Zr and 2.0 to 4 , 0 g / l Mo and most preferably 2.8 to 3.2 g / l Zr and 2.8 to 3.2 g / l Mo.
  • the aqueous solution preferably has a pH of from 1.4 to 2.7, and particularly preferably from 1.8 to 2.5, when applied by the roller application method on.
  • the aqueous, acidic solution in step c) can by prior dilution of a corresponding concentrate, preferably by a factor of 1: 30 to 1: 100, more preferably by a factor of about 1:50, preferably with water and optionally adjusting the pH value can be provided.
  • the workpieces are pickled with a mineral acid-containing aqueous, acidic solution by dipping or spraying.
  • Alkaline cleaning results in the formation of zirconium / molybdenum layers with poor volume resistivity values.
  • the compound of the invention pretreated workpieces can be pre-coated with similar pretreated or possibly otherwise, for.
  • phosphated workpieces done with surfaces of aluminum or its alloys. If intended to be joined to steel and / or galvanized and / or alloy galvanized steel parts, these parts may have bare or precoated surfaces.
  • a suitable pre-coating can, for. Example, a phosphate layer with a maximum coating weight of 2 g / m 2 or a layer of a conductive primer.
  • the pickling process must be preceded by a cleaning / degreasing stage or the pickling process must be carried out in such a way that simultaneous cleaning / degreasing takes place.
  • the latter can be done by adding surfactant to the pickling solution.
  • Phosphatier alliance are those who work with solutions based on zinc phosphate, in particular according to the low-zinc technology, or with alkali metal phosphate in the foreground.
  • the solutions may be modified by the addition of further small amounts of polyvalent cations, such as calcium, magnesium, nickel, copper or manganese.
  • chromium-free conversion treatment in particular acid solutions of the fluoro complexes of titanium, zirconium, hafnium, but also silicon, optionally containing organic polymer, are used.
  • These acidic solutions may additionally contain at least one organosilane and / or at least one hydrolysis product thereof and / or at least one condensation product thereof.
  • the at least one organosilane preferably has at least one amino group. Particularly preferably it is one which can be hydrolyzed to an aminopropylsilanol and / or to 2-aminoethyl-3-amino-propyl-silanol and / or a bis (trimethoxysilylpropyl) amine.
  • reaction primer so-called reaction primer or primer can be applied.
  • the pre-treatment of the workpieces according to the invention ensures adequate, temporary corrosion protection for longer storage times. During this time, there is no negative influence on the weldability, in particular the electrical resistance welding, or the bondability. Also, with regard to the weldability, it is ensured that the volume resistance is practically the same on all surface areas of the workpiece.
  • Workpieces in the context of the present invention are tape, sheet metal and individual parts, such as profiles.
  • the application of the solution according to step c) can be done by spraying or dipping each with or without water rinse. When applied without water rinse, it is advantageous to remove excess treatment solution by squeezing rollers. In the treatment of sheet or strip, the application of the treatment solution by the roll coater method is particularly advantageous. It allows a defined setting of the desired wet film thickness in one operation.
  • the workpiece is dried or the solution is dried.
  • Object temperatures of 30 to 90 ° C are particularly advantageous.
  • Concentrates which are diluted with low-salt water, preferably demineralized water, to the concentrations to be respectively adjusted are usually used to prepare the treatment liquids.
  • low-salt water preferably demineralized water
  • concentrations to be respectively adjusted are usually used to prepare the treatment liquids.
  • the molybdate is advantageously introduced as ammonium heptamolybdate and / or sodium heptamolybdate, preferably as ammonium heptamolybdate and particularly preferably as ammonium heptamolybdate x 7 H 2 O.
  • molybdate also includes protonated forms, in particular molybdic acid.
  • the pickling of the workpieces is done with a mineral acid-containing aqueous, acidic solution. It can be carried out electrolytically or chemically. In the case of electrolytic pickling, phosphoric acid is particularly suitable as the mineral acid.
  • the pickling by chemical means which is given preference because of the apparatus less laborious procedure in the rule, can be made with nitric acid or nitric acid / hydrofluoric acid.
  • the workpieces are pickled with a solution by spraying or dipping containing surfactant, sulfuric acid and a compound selected from the group consisting of hydrofluoric acid, phosphoric acid and iron (III) sulfate, preferably hydrogen fluoride, wherein solutions, containing 3 to 8 g / l of sulfuric acid, 50 to 150 mg / l of non-complexed free fluoride and 1 to 3 g / l of nonionic surfactant have been found to be particularly suitable.
  • Nonionic surfactants are ethylene oxide Adducts to fatty alcohols and, for example, abietic acid are particularly suitable.
  • the measurement of the free fluoride was carried out with a fluoride-sensitive electrode, wherein the calibration of the electrode was carried out with solutions whose pH was identical to that of the solution to be tested.
  • the pickling process should be carried out in such a way that a metal removal of about 0.1 to 0.6 g / m 2 workpiece surface is obtained.
  • the subsequent to the pickling of the workpieces flushing - according to step b) - is preferably carried out in several rinsing stages, and it is particularly advantageous to perform the rinse water cascade-like the workpiece in the opposite direction.
  • the last rinse step should be carried out with demineralized water.
  • the subsequent to the pickling and rinsing step treatment according to step c) prevents the re-growth of an oxide layer occurs on the workpieces with a surface made of aluminum or aluminum alloy.
  • the solution used in step c) additionally contains at least one polymer selected from the group consisting of poly (meth) acrylic acid, (meth) acrylic acid copolymers, polyvinylphosphonic acid, vinylphosphonic acid copolymers and maleic acid copolymers.
  • the (meth) acrylic acid copolymers used are preferably (meth) acrylic acid / maleic acid copolymers and the vinylphosphonic acid copolymers vinylphosphonic acid / acrylic acid copolymers.
  • polymers in particular polyacrylic acid and acrylic acid copolymers and in the latter especially acrylic acid-maleic acid copolymers are suitable.
  • the poly (meth) acrylic acid used has a number average molecular weight (MW) in the range from 4,000 to 300,000 g / mol, more preferably from 50,000 to 250,000 g / mol and most preferably from 100,000 up to 250,000 g / mol.
  • MW number average molecular weight
  • the (meth) acrylic acid copolymer used has a number average molecular weight (MW) in the range from 4,000 to 100,000 g / mol and particularly preferably from 60,000 to 80,000 g / mol.
  • MW number average molecular weight
  • the polyvinylphosphonic acid or vinylphosphonic acid copolymer used preferably has a number average molecular weight (MW) in the range from 4,000 to 70,000 g / mol and particularly preferably in the range from 10,000 to 30,000 g / mol.
  • MW number average molecular weight
  • the concentration of the at least one polymer is between 100 and 600 mg / l, preferably between 100 and 400 mg / l, more preferably between 135 and 290 mg / l and most preferably between 170 and 180 mg / l.
  • a coating weight of Zr and Mo which is more independent of the injection time and preferably largely independent of coating weight in the target range of 2 to 15 mg / m 2 can be achieved in spray application. This is particularly advantageous because even at different tape speeds similar coating weights can be achieved. Negative effects on the volume resistivity, however, are not observed by the polymer content.
  • a further advantageous embodiment of the invention provides to apply a lubricant to the workpieces.
  • a lubricant are in particular mineral oil-based forming oils, which may be fully synthetic or native, or dry lubricants based on polyethylene / polyacrylate.
  • workpieces with layers are regularly obtained which permit perfect deformation and / or gluing or, as a result of the small electrical resistance which is uniform over the workpiece surface, a perfect and trouble-free welding.
  • the workpieces are ideally suited for a subsequent permanent corrosion-protective treatment.
  • the pickling process was carried out in such a way that the pickling rate for the alloy AA 5754 was 0.05 to 0.2 g / m 2 and for the alloy AA 61 1 1 0.05 to 0.4 g / m 2 . For this treatment times between 5 and 20 seconds were required.
  • the volume resistances measured on the single sheet were about 60 ⁇ -ohms for the AA 5754 alloy and about 13 ⁇ -ohms for the AA 61 1 1 alloy.
  • the polymers A to D in Table 1 were the following:
  • A: polyacrylic acid, MW about 60,000 g / mol in colloidal solution,
  • Adhesive adhesion was determined using a modified APGE (Arizona Proving Ground Equivalent) test. To this end, two test slides (each 56.25 x 25 x 0.25 mm) were coated with a dry lubricant customary in the industry and bonded using a suitable industrial adhesive. Six such test plate pairs were then bolted at their respective ends to a chain which was subjected to a tensile stress of 2400 N. The following climate program was used per test week:
  • a sequence of steps 1. to 3. represents a cycle by definition. One cycle was passed if the adhesive bond between all of the test slides on the chain withstood. The test was passed as a whole, if at least 45 cycles were passed.
  • the phosphatability was determined by scanning electron microscope images. Thus, a "+" - in Table 3, a closed, finely crystalline phosphate layer, an "o” a closed, coarsened phosphate layer (crystals with> 20 ⁇ edge length) and a "-" a non-closed to nonexistent phosphate layer.
  • Comparative Example VB1 reveals that owing to an excessively high Zr support weight, the layer obtained in the treatment according to step c) (37 mg / m 2 at AA 5754 and 26 mg / m 2 at AA 61 1 1) has very high volume resistivities - in particular a storage of 30 days - be obtained (100 ⁇ -ohms for AA 5754 and 38 ⁇ -ohms for AA 61 1 1).
  • examples B1 to B7 show that, in compliance with the conditions essential to the invention, with regard to the type of pickling treatment, the Zr / Mo ratio, the produced coating weight, the respective Concentration and pH ranges of the treatment solutions layers with extremely good volume resistances at the same time good adhesive properties are obtained.
  • the pretreated test slides of Examples B6 and B7 and a non-pretreated bare test slide VB6 were further subjected to a multistage anticorrosive treatment consisting of the following steps: i) Alkaline purification (60 ° C., 180 s)
  • the corrosion protection of B6 and B7 is similar to that of VB6.
  • the pretreatment according to the invention therefore does not adversely affect the protection subsequently achieved by a corrosion-protective treatment.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

L'invention concerne un procédé de prétraitement de pièces ayant une surface en aluminium ou en alliages d'aluminium pour l'usinage sans copeau et/ou la liaison par soudure ou collage avec des pièces prétraitées de la même manière ou éventuellement pré-revêtues d'une autre manière ou avec des pièces en acier et/ou en acier galvanisé et/ou galvanisé par alliage, éventuellement pré-revêtues, ainsi que pour un traitement permanent de protection contre la corrosion consécutif par phosphatation, par traitement de conversion sans chrome, par application d'apprêt ou par laquage, les pièces étant a) décapées avec une solution aqueuse acide contenant un acide minéral en bain ou par pulvérisation, b) rincées avec de l'eau et c) mises en contact avec une solution aqueuse acide qui est exempte de chrome et contient Zr comme fluorure complexé ainsi que Mo comme molybdate en un rapport en poids (calculé sous forme de métal Zr/Mo) de Zr:Mo de 15:1 à 3,5 : 1, par application en bain ou par pulvérisation, si bien que, après un séchage postérieur, il en résulte un poids de couche de respectivement 2 à 5 mg/m2 de Zr et de Mo, la solution contenant 100 à 800 mg/l de Zr et 30 à 100 mg/l de Mo (calculé sous forme de métal Zr/Mo) et présentant un pH de 2,5 à 4.
EP16770231.5A 2015-09-15 2016-09-14 Prétraitement de surfaces en aluminium avec des compositions contenant du zircon et du molybdène Active EP3350357B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102015217585 2015-09-15
PCT/EP2016/071657 WO2017046139A1 (fr) 2015-09-15 2016-09-14 Prétraitement de surfaces en aluminium avec des compositions contenant du zircon et du molybdène

Publications (2)

Publication Number Publication Date
EP3350357A1 true EP3350357A1 (fr) 2018-07-25
EP3350357B1 EP3350357B1 (fr) 2024-05-01

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Country Status (11)

Country Link
US (1) US20180237919A1 (fr)
EP (1) EP3350357B1 (fr)
JP (1) JP2018527467A (fr)
KR (1) KR20180053306A (fr)
CN (1) CN108350579A (fr)
CA (1) CA2996465A1 (fr)
DE (1) DE102016217507A1 (fr)
MX (1) MX2018003246A (fr)
RU (1) RU2750923C1 (fr)
WO (1) WO2017046139A1 (fr)
ZA (1) ZA201802301B (fr)

Families Citing this family (9)

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Publication number Priority date Publication date Assignee Title
EP3545118B1 (fr) 2016-11-23 2020-08-19 Chemetall GmbH Composition et procédé de prétraitement sans chrome de surfaces d'aluminium
EP3682042B1 (fr) 2017-09-14 2021-11-10 Chemetall GmbH Procédé de prétraitement de matériaux en aluminium, en particulier de roues en aluminium
US11958989B2 (en) * 2018-09-07 2024-04-16 Rhodia Operations Method for treating surfaces of aluminum containing substrates
JP7476173B2 (ja) * 2018-09-07 2024-04-30 ケメタル ゲゼルシャフト ミット ベシュレンクテル ハフツング アルミニウム含有基材の表面を処理する方法
JP6846558B1 (ja) 2019-09-27 2021-03-24 株式会社Uacj アルミニウム合金材及びその製造方法
CN111020551B (zh) * 2019-12-30 2022-02-08 郑州大学 利用ZrO2/MoO3复合纳米膜层对铁质文物保护的方法
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WO2017046139A1 (fr) 2017-03-23
MX2018003246A (es) 2018-05-17
EP3350357B1 (fr) 2024-05-01
CN108350579A (zh) 2018-07-31
CA2996465A1 (fr) 2017-03-23
JP2018527467A (ja) 2018-09-20
KR20180053306A (ko) 2018-05-21
RU2750923C1 (ru) 2021-07-06
ZA201802301B (en) 2019-07-31
DE102016217507A1 (de) 2017-03-16
US20180237919A1 (en) 2018-08-23

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