Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/50—Multilayers
  • B05D7/51—One specific pretreatment, e.g. phosphatation, chromatation, in combination with one specific coating
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/50—Multilayers
  • B05D7/52—Two layers
• • 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
  • C23C22/34—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 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
  • C23C22/82—After-treatment
  • C23C22/83—Chemical after-treatment
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D2701/00—Coatings being able to withstand changes in the shape of the substrate or to withstand welding

Definitions

• the invention relates to a corrosion protection method for application in connection with the production of finished metallic components from organically precoated metal sheets.
• a corrosion protection coat which serves at the same time as a tie coat for the subsequent finish.
• Components joined from metal sheets may be put together from metal sheets which at that point do not have a coating providing permanent corrosion protection.
• a coating providing permanent corrosion protection composed of a conversion coat and a finish coat
• phosphating and finishing such as is customary in auto making, for example.
• the phosphating itself is only one step in a treatment sequence which in general embraces not only cleaning and rinsing stages but also pre-phosphating activation, the phosphating itself, and, frequently, a post-phosphating passivation.
• a “conversion coat” is a coat on a metal surface which is formed by “conversion treatment”, involving exposure to a “conversion solution”, and which contains not only elements from the metal surface but also from the conversion solution.
• conversion treatment Typical examples are phosphate coats or chromating coats.
• conversion treatment using for example conversion solutions based on complex fluorides of boron, silicon, titanium or zirconium. Usually these complex fluorides are employed together with organic polymers. Examples of conversion treatments of this kind are specified in DE-A-101 31 723 and the references it cites. None of these alternative methods, however, has yet been able to displace phosphating as a pre-finishing pretreatment in auto making.
• Materials of this kind are known, for example, under the name Granocoat®, Durasteel®, Bonazinc® and Durazinc®. They carry a thin organic coating over a conversion coat, a chromating or phosphating coat for example.
• the organic coating is composed of polymer systems such as epoxy or polyurethane resins, polyamides and polyacrylates, for example.
• Solid additives such as silicas, zinc dust and carbon black enhance the corrosion protection and make it possible by virtue of their electrical conductivity to carry out electrical welding and electrolytic finishing of the metal parts that are coated with coats having a thickness of from about 0.3 to about 10 ⁇ m, preferably up to about 5 ⁇ m.
• the substrate materials are generally coated in a two-stage operation in which first of all the inorganic conversion coat is produced and subsequently in a second treatment stage the organic polymer film is applied. Further information on this can be found in DE-A-100 22 075 and the references it cites.
• Metal sheets provided in the strip process with a coating based on organic polymers are therefore already being used in part in the construction of vehicle bodies, domestic appliances and pieces of furniture.
• the most stringent requirements are imposed in terms of corrosion protection and adhesion of a subsequently applied finish material, since vehicles are subject to the greatest corrosion stresses.
• At the present time there are no vehicle bodies produced exclusively from organically precoated metal sheets. Instead this material is used at best together with nonprecoated metal sheets to construct the vehicle bodies.
• the assembled bodies therefore at present still pass through the usual pretreatment process prior to finishing; that is, they are subjected to the complex operating sequence of phosphating.
• the phosphating process could in principle be replaced by a less complicated pretreatment process if the vehicle bodies were produced exclusively from organically precoated metal substrate. For that purpose, however, it is necessary to solve the problem that the assembly of bodies from organically precoated metal sheets inevitably gives rise to areas in which the organic coating is damaged or completely missing. This is the case, for example, at cut edges, at weld spots and in abraded areas.
• the corrosion conditions are different from the other conditions on the homogeneous surface at these boundary regions which combine zinc and iron.
• a different electrochemical potential is established between the potentials of zinc and iron.
• machining of the bodies gives rise to abraded areas which exhibit special conditions and therefore particular electrochemical potentials. This is because the abrading operation gives rise to an activated interface of steel (iron) with finely divided reactive zinc.
• the object addressed by the invention as part of an operation for producing finished metallic components which have been put together from metal sheets precoated with organic polymers, is to provide a simpler method than phosphating that allows corrosion protection and finish adhesion to be produced at the aforementioned sites of damage.
• the present invention in a first aspect provides a method of producing a finished component comprising metal parts made of galvanized steel, said method comprising
• the component may further include constituents made of plastic, such as may be the case, for example, in auto making.
• the metallic components of organically precoated galvanized steel may be joined to parts of plastic.
• galvanized steel embraces steels galvanized by the hot-dip method and steels galvanized electrolytically. It further embraces alloy-galvanized steels, where the coating may be composed, for example, of a zinc-nickel alloy or a zinc-aluminum alloy. The steels may have been heat-treated after galvanizing, such that an iron-zinc alloy was formed at the boundary layer between steel and zinc.
• the joining of the metal sheets to form the component in substep a) may take place in accordance with the usual techniques known in the prior art, such as by adhesive bonding, flanging, riveting, crimping and/or welding, in particular by electric welding.
• joining by means of welding owing to the associated damage to the coating based on organic polymers, leads to there being further sites on the component that are not covered by the coating based on organic polymers. These sites too are passivated in substep c), in the same way as the metal areas which come about as a result of abrading.
• the method of the invention is especially suitable for producing components comprising organically precoated metal sheets which have a coating based on organic polymers with a thickness in the range from 1 to 10 ⁇ m, the coating comprising electrically conductive particles as well as the organic polymers.
• the components can be joined by electric welding.
• coatings of this kind are contained in DE-A-197 48 764, DE-A-199 51 113, DE-A-100 22-075 and also in the references each of them cites.
• metal strips (or coils) having such coatings are available commercially under a variety of trade names.
• the passivating coat produced in substep c) should therefore not constitute a conventional zinc phosphate coat, since the present objective is to use a process sequence which is shorter and hence more economic than zinc phosphating.
• a zinc phosphate layer is not formed if the treatment solution does not simultaneously contain at least 0.3 g/l zinc ions and at least 3 g/l phosphate ions (as phosphoric acid or any protolysis stage thereof).
• the joined component can be contacted in a variety of ways with the acidic aqueous treatment solution: for example, by being immersed in the treatment solution or being sprayed with the treatment solution. After this step the water can be rinsed off, but need not necessarily be so. In other words, the method can be employed as a rinse or as a no-rinse process.
• the treatment of substep c) is not a passivation of a prior principal conversion-coat-forming operation; instead, it is the only treatment step after the components have been assembled that produces a passivating coat on the bare metal sites.
• the process sequence of the invention can be employed in particular in connection with the production of vehicle bodies, domestic appliances or pieces of furniture or a part of each thereof.
• the aqueous treatment solution in substep c) preferably has a pH of at least 2, in particular at least 2.5, to not more than 5, in particular to not more than 4. At pH values which are lower than this there is increasingly a risk of excessive pickling attack and of damage to the coating based on organic polymers. At pH values of more than 5 the pickling attack becomes increasingly so weak that the passivating coat which forms is inadequate. In actual practice it will be appreciated that the transitions are in each case fluid.
• substep c) it is possible to use chromium-free acidic aqueous treatment solutions which are known in the prior art for the large-area treatment of uncoated metal parts or metal strips. It is preferred to use a treatment solution containing in total at least 0.01 g/l, preferably at least 0.025 g/l, and up to 10 g/l, preferably up to 1 g/l, in particular up to 0.5 g/l, Ti and/or Zr and/or Si ions and also containing at least an amount of fluoride such that the atomic ratio of Ti to F and/or of Zr to F and/or of Si to F is in the range from 1:1 to 1:6, and which additionally contains at least 0.005 g/l, preferably at least 0.01 g/l, and up to 20 g/l, preferably up to 1 g/l, organic polymers.
• the stated Ti, Zr and/or Si ions may be used completely in the form of hexafluoro complexes such as, for example, the hexafluoro acids, or their salts which are water-soluble within the stated concentration range, such as the sodium salts, for example. In that case the atomic ratio is 1:6. It is also possible, however, to use complex compounds in each of which there are less than six fluoride ions joined to the central elements Ti, Zr or Si. These compounds may be formed automatically in the treatment solution when not only hexafluoro complexes of at least one of the central elements Ti, Zr or Si but also at least one further compound of one of these central elements are added to said treatment solution.
• Suitable such further compounds include nitrates, carbonates, hydroxides and/or oxides of the same central element or of another of the three stated central elements.
• the treatment solution may comprise hexafluorozirconate ions and also (preferably colloidal) silica (SiO 2 ) or reaction products thereof. Unreacted silica may be in suspension in the treatment solution.
• a treatment solution of this kind can also be obtained by using hydrofluoric acid or its salts (acidic salts where appropriate) together with such compounds of Ti, Zr and/or Si as are able to form fluoro complexes therewith. Examples are the aforementioned nitrates, carbonates, hydroxides and/or oxides.
• an amount of Ti, Zr and/or Si as central metal, and an amount of fluoride, which are such that the atomic ratio of central metal to fluoride is less than or equal to 1:2, in particular less than or equal to 1:3.
• the atomic ratio may also be less than 1:6 if the treatment solution contains a greater amount of fluoride, in the form for example of hydrofluoric acid or its salts, than is required stoichiometrically to form the hexafluoro complexes of the central metals Ti, Zr and/or Si.
• the atomic ratio may be as low as 1:12 or 1:18 or even lower, if a corresponding excess of fluoride is used, in other words two or three times or even more times the amount required to form the hexafluoro complexes in full.
• treatment solutions comprising combinations of ingredients that are known in the prior art: for example, in accordance with U.S. Pat. No. 5,129,967, a treatment solution which comprises at least the following components in water:
• treatment solutions in which the organic polymers are selected from homopolymers and copolymers of vinylpyrrolidone.
• Treatment solutions of this kind are described in DE-A-100 05 113 and DE-A-101 31 723.
• these copolymers may include, further to vinylpyrrolidone, one or more other monomers. They may therefore be present, for example, as copolymers of 2 components or as copolymers of 3 components (i.e., terpolymers). In addition it is possible to use mixtures of homopolymers and two-component copolymers, homopolymers and terpolymers or two-component copolymers and terpolymers.
• Suitable homopolymers or copolymers of vinylpyrrolidone include the polymers listed in Table 1 and/or polymers of the monomers indicated therein. Copolymers of vinylpyrrolidone with monomers containing caprolactam groups or imidazole groups are particularly preferred.
• the preferred treatment solutions described above preferably have a temperature in the range from 20 to 45° C., in particular from 30 to 40° C. This treatment solution is contacted with the cleaned joined component for a time in the range from 1 to 5 minutes, in particular from 2 to 3 minutes.
• the treatment solutions to be used ought by definition to be free from chromium. It is further preferred in this context for the acidic aqueous treatment solution to contain no transition-group metals (transition metals) other than metals from transition group 4 of the Periodic Table (in the form, for example, of complex fluorides of Ti and/or Zr). This simplifies the treatment of wastewaters obtained.
• transition metals transition metals
• This finish material may be selected, for example, from a dip-coating material, an electrodeposition material or a powder coating material.
• the present invention provides a finished component comprising metal parts made of galvanized steel which is obtainable by the method described above.
• metal parts of the component are composed of organically precoated galvanized steel.
• the component may also include constituents made of plastic, such as may be the case in auto making, for example.
• Granocoat® products specified in the examples are coating systems for galvanized steel based on organic polymers and conductivity pigments, as elucidated in more detail in the description above. These products are described in patent applications DE-A-100 22 075 (Granocoat® ZE) and DE-A-100 22 075 (Granocoat® S).)
• test results show that with the shorter process sequence of the invention the results achieved at least match those achieved with a zinc phosphating process. In terms of tendency the results in accordance with the method of the invention are in fact better than those obtained with a zinc phosphating process.

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• Chemical & Material Sciences (AREA)
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• Wood Science & Technology (AREA)
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• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Mechanical Engineering (AREA)
• Metallurgy (AREA)
• Organic Chemistry (AREA)
• Application Of Or Painting With Fluid Materials (AREA)
• Chemical Treatment Of Metals (AREA)
• Laminated Bodies (AREA)

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Citations (7)

• 2003
  • 2003-11-14 DE DE10353149A patent/DE10353149A1/de not_active Withdrawn
• 2004
  • 2004-09-23 AT AT04022644T patent/ATE516088T1/de active
  • 2004-09-23 EP EP04022644A patent/EP1531012B1/de not_active Not-in-force
  • 2004-11-12 US US10/987,998 patent/US20050121113A1/en not_active Abandoned

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