EP3390690A1 - Verfahren zur passivierung einer oberfläche eines metallbauteils - Google Patents
Verfahren zur passivierung einer oberfläche eines metallbauteilsInfo
- Publication number
- EP3390690A1 EP3390690A1 EP17710122.7A EP17710122A EP3390690A1 EP 3390690 A1 EP3390690 A1 EP 3390690A1 EP 17710122 A EP17710122 A EP 17710122A EP 3390690 A1 EP3390690 A1 EP 3390690A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- concentration
- conversion layer
- component
- passivation
- 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
Links
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
- C23C22/07—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 phosphates
- C23C22/08—Orthophosphates
- C23C22/22—Orthophosphates containing alkaline earth metal cations
-
- 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
- C23C22/68—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 solutions with pH between 6 and 8
Definitions
- the invention relates to a method for passivating a surface of a metal component according to the preamble of patent claim 1 and to a passivation solution for forming a conversion layer for the surface of the metal component according to patent claim 16.
- metal components in particular of light metal components, is common practice across industries.
- vehicle construction for example, vehicle bodies in mixed construction, for example
- Alloy and sheet steel parts are manufactured to a
- aluminum or magnesium materials or alloys thereof can be used as light metal.
- vehicle bodies manufactured in mixed construction there is a risk of contact corrosion between the light metal components (off
- Method is generated in a passivation step using an aqueous Passivitationslosung on the surface of the metal component, a calcium phosphate-containing conversion layer.
- the conversion layer has oxides and hydroxides as well as carbonates of the component material and the passivation solution.
- the passivation can be one
- Process chain for painting vehicle bodies process technology are upstream, as known from DE 196 30 289 C2.
- Magnesium alloy is.
- the process can produce a nickel coating of uniform thickness.
- From DE 37 15 663 A1 is a Andosier solution for anodic oxidation of magnesium or
- Magnesium alloys known. From JP 2009-228087 a method for coating a light metal component made of a magnesium alloy is known.
- the object of the invention is to provide a method for passivating the surface of a metal component, in which compared to the prior art, a simple and improved passivation is possible.
- the passivation solution for the formation of the conversion layer has at least one substance acting as chelate complexing agent (ie chelate ligand). This results in a later-described film forming mechanism in which the conversion layer formed is less cracked compared to the prior art.
- Chelating agents ie chelating ligands work. These plurality of different chelating agents can compete with each other in the conversion layer formation, so that the film forming mechanism is impaired, which may lead to the crack structure in the conversion layer.
- Chelate complexing agent substance is initiated. Of the
- the layering mechanism is not affected by other competing substances which may also act as chelating agents.
- the conversion layer is thereby formed with a closed, low-crack layer morphology, whereby its protective effect is improved. Substantially the same effect is achieved when the plurality of chelating agents are limited to a few Chelating agent is limited to about two or three Chelatkomplexsentner substances.
- the chelate complexing agent used may preferably be an organic substance having optionally deprotonated functional groups with one or more lone pairs of electrons, that is to say
- an organic substance for example, an organic acid or its salts, an amino acid or a suitable vitamin comes into question.
- the organic acid contained in the passivation solution may be a tartaric acid, an acetic acid or L-arginine.
- the substance acting as chelate complexing agent may preferably be contained in the passivating solution at a concentration in the range of 1-20 mmol / l.
- Possible further groups of chelating agents in addition to carboxylic acids (organic acids) are also: alcohols, phenols, naphthols, enols, thiols, sulfonic acid, phosphoric acid esters, phosphonic acid.
- the chelating agent-substance (hereinafter exemplified by tartaric acid) contained in the passivating solution makes it possible to form a layer-forming mechanism that is perfect in comparison with the prior art for forming the conversion layer.
- Tartaric acid as a chelating agent in which the Ca 2+ ions coordinating in the passivation solution are complexed in the respective tartaric acid molecule to form a chelate complex.
- the chelate complex is briefly physically reversibly adsorbed on optionally deprotonated functional groups, that is, for example via OH end groups, to the metallic component surface.
- the bound in the chelate Ca 2+ ions are therefore transported to the metallic component surface. There it reacts with the phosphates dissolved in the passivation solution and forms the calcium phosphate-containing conversion layer. Subsequently, a desorption of the chelate complexing agent (that is the des
- Penetration resistance therefore behaves inversely proportional to the corrosion currents.
- the passive behavior of the conversion layer is increased due to the substantially closed, low-crack layer structure of the conversion layer.
- the formed with the passivated surface metal component can be used across industries.
- the metal component can be used in the medical field. Alternatively, that is
- Metal component optionally used in the automotive sector, and that is visible within the vehicle or as an externally visible outer part.
- the metal component can be realized as a vehicle-inner-side display frame, an aggregate part, a chassis part or a component of a seat frame structure.
- a component material made of aluminum results with the
- Passivation Solution A compact calcium phosphate and aluminum hydroxide / oxide coating with amino acids.
- the layer morphology is substantially closed, that is, at least low-crack, formed.
- Magnesium hydroxide / oxide-containing coating whose layer morphology is also substantially closed and formed low-crack.
- the passivation solution may preferably comprise at least the following constituents as activators for activating the surface of the component: NaCl having a concentration between 5500 and 7500, in particular 6400 mg / l; and or
- KCl with a concentration between 300 and 500, in particular
- the passivation MgS0 4 -7H 2 0 may be at a concentration between 100 and 400, comprise, in particular 200 mg / l.
- the passivation layer may preferably contain calcium phosphates.
- the conversion layer may contain carbonaceous constituents.
- the passivation solution may contain NaHCO 3 .
- the formation of carbonate also depends on possibly supplied CO 2 .
- the passivation solution may be in a particularly preferred
- Chelate complexing agent with in particular 1 to 20 mmol / l can be carried out at a pH of about 7. In this case, the coating reaction is slow. Alternatively, the coating reaction can also take place in the acidic range. The coating reaction can be achieved by increasing the
- the coating process can preferably by means of a pH reduction (pH of 1 to 5) and by means of a temperature increase of normal
- Room temperature can be accelerated by 15 ° to 80 ° C.
- the metal component may be a vehicle part, which is first pretreated with the passivation solution according to the invention to form the conversion layer.
- the conversion layer of the component can be covered with at least one further layer in a subsequent coating process.
- the coating process can be a first
- Coating step in which a KTL layer, that is, an organic protective layer is formed. This is done in one
- Coating step is then applied a powder coating. This is done in a powder coating process under applied
- the metal component for example as a
- the metal body mounted on the green body is already precoated with a layer structure, namely with the conversion layer, the cathodic electrostatic layer and the powder coating.
- the metal component is thus electrically insulated, so that the body in the Rohkarosserie-
- Figs. 1 b and 1 c are views each illustrating the film formation mechanism for forming a conversion layer
- Body part 3 shown.
- the body part 3 made of light metal, such as aluminum, magnesium or an alloy thereof.
- the layer structure 1 directly on the workpiece surface 25 of the light metal component 3, a conversion layer 5, which serves for passivation and corrosion protection.
- Conversion layer 5 is covered by a KTL layer 6. On this a powder coating 7 is formed, on which a conventional automotive, multi-layer paint system 9 (in Fig. 1a for reasons of
- the conversion layer 5 has a substantially closed, low-crack layer morphology.
- the conversion layer 5 is also designed so that in a later described KTL coating process for a sufficient residual conductivity between a KTL immersion bath and the light metal material of the component 3 is provided.
- Conversion layer 5 actually has a layer thickness which is in the ⁇ range.
- a series paint process carried out in a painting installation will be described, in which a passivation solution according to the invention is used: Accordingly, in FIG. 2, as pretreatment steps, an (optional) mechanical treatment, for example, takes place Grind. Subsequently, a wet chemical pretreatment, that is, a degreasing and a pickling, performed. This is followed by a passivation step, in which the metal component 3 is immersed, for example, in a dipping bath of the passivation solution.
- the passivation solution contains at least the following main components: NaCl at 6400 mg / l
- NaCl and KCl in the passivation solution serve to activate the metal surface 25.
- the components NaH 2 PO 4 and CaCb support the coating process by incorporating the Ca 2+ and PO 4 3 " ions into the conversion layer 5.
- the tartaric acid effects the following with reference to FIGS. 1 b and 1 c
- the Ca 2+ ions are bound by electrostatic attraction (indicated by dashed lines in FIGS. 1 b and 1 c).
- amino acids / vitamins can thus bind ions.
- an amino acid for example, the amino acid L-arginine
- a suitable vitamin as a chelating agent in the
- End groups COOH end groups, PO 4 3 " end groups, SH end groups or OH end groups.
- the chelate complex 8 is attached via functional groups, that is to say via OH end groups, to the Surface 25 of the metal component 3 briefly adsorbed physically reversible (in Fig. 1 c indicated by dashed arrow).
- Chelate complex 8 bound Ca 2+ ions are therefore included in the
- Chelate complexing agent that is, the chelating ligand
- the tartaric acid (or other suitable substance) is preferred as the sole chelating agent in the
- Chelating agent-substance acts. That of the tartaric acid
- Chelate complexing agents can act. In this way, the
- the conversion layer 5 therefore has an improved protective effect compared to conversion layers with crack structures.
- the passivation solution may also contain several different chelating agent substances.
- the conversion layer 5 according to the invention also has carbonate-containing layer constituents. These are provided in the passivation solution by the component NaHCO 3 and CO 2 (from the atmosphere). Overall, it is therefore in the inventive
- Passivitations preferably to an aqueous treatment liquid whose pH is in the range of about 7 or in the acidic range.
- the passivation is preferably carried out in the immersion bath at room temperature.
- Treatment time depends on the set pH, the
- Coating process can be accelerated by means of a pH reduction to a pH of 1 to 5 and / or by increasing the temperature by 15 to 80 ° C.
- the coated with the conversion layer 5 component 3 is in
- the KTL is done in common practice in the dipping process, in which between the body 15 and the
- the component 3 passes through a continuous furnace at a predetermined conveying speed, in which the KTL layer 6 at process temperatures in the range of for example 180 ° C. is burned. Subsequently, in process step II in a
- Coating station 20 carried out a powder coating, in which the layer 7 (Fig. 1) is applied to the component 3.
- the layer 7 (Fig. 1) is applied to the component 3.
- Powder coating 20 the paint particles are transported by an electrostatic field of live pointed heads to the grounded component 3. Subsequently, in a further station 19, a baking process takes place in a continuous furnace.
- the light metal component 3 is added in an exemplary possible application as a visible vehicle outer part in a joining process (for example, gluing and / or screws) to a shell body not yet painted.
- the green body 15 is conveyed in a continuous process in a body painting plant (see Fig. 4).
- the body provided with the primer body 15 is led to another coating station 29, in which a KTL process takes place.
- the KTL process 29 is likewise a continuous furnace 31
- Coating station 33 applied a conventional automotive four-layer paint system 9, which is subsequently subjected to a baking process 35.
- the body painting process shown in FIG. 4 is carried out with already pre-coated light metal component 3. That means that
- Light metal component 3 is electrically insulated, so that the applied in Rohkosheie- Lackier Anlagen KTL layer no longer adhere, whereas the conventional automotive paint system 9 (that is, a Four-layer structure) readily on the powder coating 7 of
- Figs. 5 to 7 is in views corresponding to FIG. 1 the
- Light metal component 3 shown in different process steps. Thus, in FIG. 5, the light metal component 3 with cleaned and exposed metallic surface 25 is shown. In Fig. 6, the light metal component 3 is shown after passivation and rinsing or drying.
- the conversion layer 5 is on the surface 25 of the
- the conversion layer 5 as a sole layer that is, in the single-layer structure without additional intermediate and outer layers
Landscapes
- 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)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102016002852.1A DE102016002852A1 (de) | 2016-03-10 | 2016-03-10 | Verfahren zur Passivierung einer Oberfläche eines Metallbauteils |
| PCT/EP2017/000240 WO2017153036A1 (de) | 2016-03-10 | 2017-02-20 | Verfahren zur passivierung einer oberfläche eines metallbauteils |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP3390690A1 true EP3390690A1 (de) | 2018-10-24 |
| EP3390690B1 EP3390690B1 (de) | 2022-04-27 |
| EP3390690B8 EP3390690B8 (de) | 2022-06-29 |
Family
ID=58266545
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP17710122.7A Active EP3390690B8 (de) | 2016-03-10 | 2017-02-20 | Passivierungslösung zur passivierung einer oberfläche eines metallbauteils |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP3390690B8 (de) |
| DE (1) | DE102016002852A1 (de) |
| WO (1) | WO2017153036A1 (de) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102017107529A1 (de) * | 2017-04-07 | 2018-10-11 | Lisa Dräxlmaier GmbH | Verfahren zur Korrosionsinhibierung von Metallen und Temperierungssystem für ein metallisches Werkzeug |
| DE102017011379A1 (de) | 2017-12-11 | 2019-06-13 | Audi Ag | Anti-Korrosionsbeschichtung für metallische Substrate |
| DE102019200848A1 (de) * | 2019-01-24 | 2020-07-30 | Audi Ag | Beschichtungsanordnung für Mg-Bauteile |
| DE102019131441B3 (de) * | 2019-11-21 | 2020-12-31 | Audi Ag | Elektronikgehäuse zur Aufnahme einer elektrischen Komponente |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL91161C (de) * | 1952-08-28 | |||
| US4744872A (en) | 1986-05-30 | 1988-05-17 | Ube Industries, Ltd. | Anodizing solution for anodic oxidation of magnesium or its alloys |
| DE19630289C2 (de) | 1996-07-26 | 2002-03-14 | Audi Ag | Verfahren zum Lackieren von Fahrzeugkarosserien |
| JP5520439B2 (ja) * | 2007-11-01 | 2014-06-11 | 日本パーカライジング株式会社 | 表面調整アルミニウム鋳造物の製造方法 |
| JP2009228087A (ja) | 2008-03-25 | 2009-10-08 | Hiroshima Univ | マグネシウム合金被膜及びその製造方法 |
| JP5517024B2 (ja) * | 2009-02-02 | 2014-06-11 | 独立行政法人物質・材料研究機構 | Mg基構造部材 |
| ITMI20131265A1 (it) | 2013-07-29 | 2013-10-28 | Ivan Fischetto | Sistema perfezionato di pretrattamento ai fini della nichelatura chimica e dell'eventale ulteriore trattamento superficiale del magnesio ( e di tutte le sue leghe conosciute) |
| DE102014005444A1 (de) | 2014-04-11 | 2015-10-15 | Audi Ag | Verfahren zur Passivierung einer metallischen Oberfläche |
-
2016
- 2016-03-10 DE DE102016002852.1A patent/DE102016002852A1/de not_active Ceased
-
2017
- 2017-02-20 WO PCT/EP2017/000240 patent/WO2017153036A1/de not_active Ceased
- 2017-02-20 EP EP17710122.7A patent/EP3390690B8/de active Active
Also Published As
| Publication number | Publication date |
|---|---|
| WO2017153036A1 (de) | 2017-09-14 |
| DE102016002852A1 (de) | 2017-09-14 |
| EP3390690B1 (de) | 2022-04-27 |
| EP3390690B8 (de) | 2022-06-29 |
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