EP1978131B2 - Means for manufacturing corrosion protection coats on metal surfaces - Google Patents
Means for manufacturing corrosion protection coats on metal surfaces Download PDFInfo
- Publication number
- EP1978131B2 EP1978131B2 EP07105237.7A EP07105237A EP1978131B2 EP 1978131 B2 EP1978131 B2 EP 1978131B2 EP 07105237 A EP07105237 A EP 07105237A EP 1978131 B2 EP1978131 B2 EP 1978131B2
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- EP
- European Patent Office
- Prior art keywords
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- composition according
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- comp
- 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.)
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- 229910052751 metal Inorganic materials 0.000 title claims description 32
- 239000002184 metal Substances 0.000 title claims description 32
- 238000005260 corrosion Methods 0.000 title claims description 19
- 230000007797 corrosion Effects 0.000 title description 18
- 238000004519 manufacturing process Methods 0.000 title description 9
- 239000000243 solution Substances 0.000 claims description 50
- 239000000203 mixture Substances 0.000 claims description 28
- 238000011282 treatment Methods 0.000 claims description 27
- 239000002105 nanoparticle Substances 0.000 claims description 23
- 239000000126 substance Substances 0.000 claims description 19
- 150000001450 anions Chemical class 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 229910052736 halogen Inorganic materials 0.000 claims description 13
- 150000002367 halogens Chemical class 0.000 claims description 13
- 238000011065 in-situ storage Methods 0.000 claims description 11
- -1 oxo cations Chemical class 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 230000001590 oxidative effect Effects 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 101100396546 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) tif-6 gene Proteins 0.000 claims description 2
- 229910004074 SiF6 Inorganic materials 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000004973 alkali metal peroxides Chemical class 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 229910001507 metal halide Inorganic materials 0.000 claims description 2
- 150000005309 metal halides Chemical class 0.000 claims description 2
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 150000001451 organic peroxides Chemical class 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 159000000001 potassium salts Chemical class 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 19
- 238000003756 stirring Methods 0.000 description 18
- 239000003795 chemical substances by application Substances 0.000 description 16
- 229910010298 TiOSO4 Inorganic materials 0.000 description 13
- KADRTWZQWGIUGO-UHFFFAOYSA-L oxotitanium(2+);sulfate Chemical compound [Ti+2]=O.[O-]S([O-])(=O)=O KADRTWZQWGIUGO-UHFFFAOYSA-L 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000000576 coating method Methods 0.000 description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- 229910003708 H2TiF6 Inorganic materials 0.000 description 6
- 229910020491 K2TiF6 Inorganic materials 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 238000002161 passivation Methods 0.000 description 5
- 229910001297 Zn alloy Inorganic materials 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 4
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 3
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 2
- 229910003638 H2SiF6 Inorganic materials 0.000 description 2
- 229910003899 H2ZrF6 Inorganic materials 0.000 description 2
- 229910020440 K2SiF6 Inorganic materials 0.000 description 2
- 229910020148 K2ZrF6 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical class [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- ZEFWRWWINDLIIV-UHFFFAOYSA-N tetrafluorosilane;dihydrofluoride Chemical compound F.F.F[Si](F)(F)F ZEFWRWWINDLIIV-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 238000004091 panning Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
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
- C23C22/34—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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/04—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly acid liquids
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/06—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly alkaline liquids
Definitions
- the present invention relates to compositions for the production of anticorrosive coatings on metal surfaces, to processes for the preparation of such compositions and to their use.
- compositions of the invention are used in particular for the production of corrosion-protective conversion layers or passivation layers on metal surfaces, such as the surfaces of pure metal substrates such as zinc, aluminum, magnesium or their alloys and galvanically produced surfaces of zinc or their alloys.
- Metal parts are coated to protect against corrosion, for example, galvanically with base metals, such.
- base metals such as zinc, nickel, chromium, aluminum, magnesium and alloys of the aforementioned, and the corrosion resistance of the metal coating by forming a conversion layer, often a passivation layer further improved.
- the metal surfaces are often treated with solutions containing chromium (VI).
- chromium (VI) compounds due to the high toxicity and carcinogenicity of chromium (VI) compounds, more recent attempts have been made to prepare such conversion layers with chromium (III) -containing solutions. These chromium (III) -containing treatment liquids are added to increase the corrosion protection effect of the prepared conversion layers many times high amounts of cobalt (II) compounds.
- Recent processes produce protective layers with an organosilicon-based binder system to which corrosion inhibiting additives based on molybdenum, tungsten, titanium, zirconium, vanadium and other metals are added.
- the US-A-6,524,403 describes a chromium-free composition for improving the corrosion resistance of zinc or zinc alloy surfaces, which composition contains a source of titanium ions or titanates, an oxidizer and fluorides, and Group II metal compounds, and the composition is substantially free of silicates and silica. Strontium is used in particular as Group II metal.
- the EP 0 760 401 discloses an anticorrosive composition containing an oxidizing agent, a silicate and / or silica and metal cations selected from Ti, Zr, Ce, Sr, V, W and Mo, oxime metal anions thereof and / or fluorometal anions thereof.
- the previously known chromium-free corrosion inhibitors have the disadvantage that they either do not provide sufficient corrosion protection properties of the conversion layers or are not sufficiently stable to use them in a continuous process or both.
- the object of the present invention was to overcome the disadvantages of the known in the prior art means for producing anticorrosive layers or conversion layers on metal surfaces, in particular surfaces of zinc, aluminum, magnesium or their alloys, wherein the means free of chromium and cobalt should be.
- the agent according to the invention is characterized inter alia by containing in situ generated nanoparticles which are stable or at least metastable.
- a conversion layer or passivation layer is formed in the treatment of metal surfaces with the agent according to the invention.
- the nanoparticles generated in situ in the treatment solution are incorporated into the conversion layer during the formation of the conversion layer, thereby resulting in a particularly high corrosion protection effect of the treated metal surfaces.
- these nanoparticles are generated in situ by hydrolysis or oxidation of the substances contained in the starting solution. The nanoparticles are not added to the solution as already existing nanoparticulate particles from outside.
- inventively generated in situ nanoparticles are better incorporated into the conversion layers and thereby these layers are denser and thus more corrosion resistant than those which can be produced by applying a corrosion protection solution were added to the nanoparticles from the outside, for example in the form of a Silica or silicate solution.
- the nanoparticles in the agent according to the invention are carried out in situ produces physical and / or chemical treatment of the starting solution, resulting in a colloidal solution.
- a Tyndall lamp By means of a Tyndall lamp, the formation of nanoparticles can be easily detected.
- the nanoparticles have an average particle diameter ⁇ 500 nm.
- the nanoparticles are formed from the halogen complex anions and / or oxo cations by hydrolysis or oxidation.
- the nanoparticles thus consist essentially of the oxides of the metals or metalloids.
- the formation of nanoparticles in situ by the physical and / or chemical treatment is carried out by bringing the initially present equilibrium state of the starting solution in an imbalance state and the system in a stabilized metastable state.
- the transition from the equilibrium state to an imbalance state can be effected by changing the temperature, changing the ion concentration, changing the pH, changing the pressure, supersaturating the solution, stirring the solution, adding an oxidizing agent and / or adding a reducing agent.
- the formation of the nanoparticles takes place in situ by supersaturation of the solution and / or stirring of the solution.
- composition of the invention may be provided in various forms and stages of completion prior to the treatment of metal surfaces as a commercial product.
- the agent of the invention is provided as a concentrate which is to be diluted before use.
- the product according to the invention is suitable as a commercial product as soon as the aqueous solution containing oxo-cations and halogen complex anions has been prepared according to step A) and the nanoparticles according to B) have been formed in situ.
- an oxidative substance is added selected from hydrogen peroxide, organic peroxides, alkali metal peroxides, persulfates, perborates, nitrates and mixtures thereof, the addition of hydrogen peroxide as oxidative substance is particularly preferred.
- the addition of the oxidative substance is expediently carried out before the use of the agent according to the invention for the production of anticorrosion coatings, wherein the agent according to the invention can already be provided with the oxidative substance contained therein or the oxidative substance is added shortly before the use of the agent according to the invention at the manufacturer of the anticorrosive coatings ,
- the addition of the oxidative substance before the use of the agent according to the invention for the production of anticorrosive coatings causes, inter alia, a pre-passivation of the metallic surface, in particular a zinc or zinc alloy surface, which is advantageous because the treatment solution can be extremely aggressive against the metallic surface and dissolve it at least partially could.
- the pH is adjusted by means of an acid or base to a value in the range from 0.5 to 5.0, preferably in the range from 1.0 to 3.0, more preferably adjusted in the range of 1.3 to 2.0.
- a value in the range from 0.5 to 5.0 preferably in the range from 1.0 to 3.0, more preferably adjusted in the range of 1.3 to 2.0.
- the agent according to the invention is prepared by the formation of nanoparticles according to step B) at a temperature in the range of room temperature to 100 ° C, preferably in the range of 30 ° C to 80 ° C, more preferably in the range from 35 ° C to 50 ° C is performed.
- a temperature in the range of room temperature to 100 ° C, preferably in the range of 30 ° C to 80 ° C, more preferably in the range from 35 ° C to 50 ° C is performed.
- a temperature in the range of room temperature to 100 ° C, preferably in the range of 30 ° C to 80 ° C, more preferably in the range from 35 ° C to 50 ° C is performed.
- a temperature in the range of room temperature to 100 ° C, preferably in the range of 30 ° C to 80 ° C, more preferably in the range from 35 ° C to 50 ° C is performed.
- Too low a temperature nanoparticles are formed at an uneconomically slow rate.
- the agent is prepared by adding the halogen complex anions b) to the aqueous solution in step A) in the form of their metal salts, preferably their alkali metal salts, more preferably their sodium and potassium salts.
- their metal salts preferably their alkali metal salts, more preferably their sodium and potassium salts.
- halogen complex anions b) fluoroanions selected from BF4 ⁇ 1->, TiF6 ⁇ 2->, ZrF6 ⁇ 2->, SiF6 ⁇ 2->, AIF6 ⁇ 3-> and mixtures thereof.
- further metal salts are added to the aqueous solution in stage A), preferably salts of the metals B, Ti, Zr, Si and / or Al.
- the metals are added in the form of the metal halides, metal nitrates and / or metal sulfates.
- the aqueous solution prepared in step A) contains the oxo cations in a concentration of 0.1 to 0.5 wt .-%, preferably in a concentration of 0.1 to 0.3 wt. -%.
- the aqueous solution prepared in step A) contains the halogen complex anions in a concentration of 0.1 to 3.0 wt .-%, preferably in a concentration of 0.5 to 2.0% by weight.
- the agent of the invention may be provided as a concentrate to be diluted before use.
- the agent according to the invention can already be provided in the concentration or dilution suitable for the application.
- the solution obtained in step B) is expediently diluted with water in a ratio of 1: 3 to 1: 5 before or after the addition of an oxidative substance in step C).
- composition according to the invention for the production of anticorrosive coatings is carried out by direct treatment of the metal surfaces with the agent, preferably by immersing or pivoting the objects with metal surfaces in the or the agent.
- Application by dipping or panning is preferably carried out at a temperature of the treatment bath in the range of 20 to 100 ° C, preferably 30 to 70 ° C, more preferably 40 to 60 ° C, and most preferably about 50 ° C.
- the most suitable treatment time for the production of anticorrosive coatings by immersing or pivoting the objects with metal surfaces in the treatment or the treatment varies depending on various parameters, such as.
- the composition of the treatment solution, the treatment temperature, the type of metal surface and the degree of corrosion protection desired is in the range of 10 to 120 seconds, preferably in the range of 20 to 60 seconds.
- compositions according to the invention and comparative compositions an aqueous solution of oxo anions a) is prepared.
- the halogen complex anion component b in this example a fluoroanion component
- this solution is subjected to physical and / or chemical treatment by vigorous stirring (propeller stirrer, 700 to 1000 rpm).
- the formation of nanoparticles is checked by means of a Tyndall lamp.
- the solution obtained is made up to 1 l with water.
- Table 1 shows that without treatment of the solutions by stirring (solutions 1b to 11b) no Tyndall effect was observed and thus no formation of nanoparticles was achieved. The same was observed when the fluoroanion component was used in the form of its free acid with and without stirring (solutions 2a, 2b, 4a, 4b, 7a, 7b, 9a, 9b, 11a and 11b).
- Galvanized sheets were treated with the previously prepared and shown in Table 1 treatment solutions by immersion in the solutions for 60 seconds at 50 ° C. The sheets were then rinsed with water and subjected to a corrosion test according to DIN 50021 SS (salt spray test) for drumware and the duration of occurrence of i) first signs of corrosion and ii) 5% white rust compared. The results are shown in Table 2.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Chemical Treatment Of Metals (AREA)
Description
Die vorliegende Erfindung betrifft Mittel zur Herstellung von Korrosionsschutzschichten auf Metalloberflächen, Verfahren zur Herstellung solcher Mittel und deren Verwendung.The present invention relates to compositions for the production of anticorrosive coatings on metal surfaces, to processes for the preparation of such compositions and to their use.
Die erfindungsgemäßen Mittel dienen insbesondere der Erzeugung von korrosionsschützenden Konversionsschichten bzw. Passivierungsschichten auf Metalloberflächen, wie den Oberflächen reiner Metallsubstrate wie Zink, Aluminium, Magnesium oder deren Legierungen und galvanisch erzeugten Oberflächen aus Zink oder deren Legierungen.The compositions of the invention are used in particular for the production of corrosion-protective conversion layers or passivation layers on metal surfaces, such as the surfaces of pure metal substrates such as zinc, aluminum, magnesium or their alloys and galvanically produced surfaces of zinc or their alloys.
Metallteile werden zum Schutz vor Korrosion beispielsweise galvanisch mit unedlen Metallen beschichtet, wie z. B. Zink, Nickel, Chrom, Aluminium, Magnesium und Legierungen der vorgenannten, und die Korrosionsbeständigkeit der Metallbeschichtung durch Erzeugung einer Konversionsschicht, häufig einer Passivierungsschicht, weiter verbessert. Zur Erzeugung einer Passivierungsschicht werden die Metalloberflächen vielfach mit Chrom(VI) enthaltenden Lösungen behandelt. Aufgrund der hohen Toxizität und Kanzerogenität von Chrom(VI)-Verbindungen ist man in jüngerer Zeit jedoch dazu übergegangen, derartige Konversionsschichten mit Chrom(III)-haltigen Lösungen herzustellen. Diesen Chrom(III)-haltigen Behandlungsflüssigkeiten werden zur Erhöhung der Korrosionsschutzwirkung der hergestellten Konversionsschichten vielfach hohe Mengen an Kobalt(II)-Verbindungen zugegeben. Allerdings stellen auch diese Behandlungslösungen ein Problem dar, da sowohl Chrom(III) als auch Kobalt(II) hinsichtlich ihrer Toxizität nicht unbedenklich sind und aufgrund von analytischen Problemen nicht sichergestellt werden kann, daß die Konversionsschichten frei von Chrom(VI) sind. Daher besteht ein dringender Bedarf, vollständig chrom- und kobaltfreie Korrosionsschutzschichten herzustellen.Metal parts are coated to protect against corrosion, for example, galvanically with base metals, such. As zinc, nickel, chromium, aluminum, magnesium and alloys of the aforementioned, and the corrosion resistance of the metal coating by forming a conversion layer, often a passivation layer further improved. To produce a passivation layer, the metal surfaces are often treated with solutions containing chromium (VI). However, due to the high toxicity and carcinogenicity of chromium (VI) compounds, more recent attempts have been made to prepare such conversion layers with chromium (III) -containing solutions. These chromium (III) -containing treatment liquids are added to increase the corrosion protection effect of the prepared conversion layers many times high amounts of cobalt (II) compounds. However, these treatment solutions are also a problem, since both chromium (III) and cobalt (II) are not acceptable in terms of their toxicity and can not be ensured due to analytical problems that the conversion layers are free of chromium (VI). Therefore, there is an urgent need to produce completely chromium and cobalt-free anticorrosive coatings.
Neuere Verfahren erzeugen Schutzschichten mit einem Bindemittelsystem auf organischer bzw. siliziumorganischer Basis, denen korrosionshemmende bzw. schichtverstärkende Zusatzstoffe auf Basis von Molybdän, Wolfram, Titan, Zirkonium, Vanadium und anderen Metallen zugegeben werden.Recent processes produce protective layers with an organosilicon-based binder system to which corrosion inhibiting additives based on molybdenum, tungsten, titanium, zirconium, vanadium and other metals are added.
Die
Die
Die bislang bekannten chromfreien Korrosionsschutzmittel haben den Nachteil, daß sie entweder keine hinreichenden Korrosionsschutzeigenschaften der Konversionsschichten liefern oder nicht ausreichend stabil sind, um sie in einem kontinuierlichen Verfahren einzusetzen oder beides.The previously known chromium-free corrosion inhibitors have the disadvantage that they either do not provide sufficient corrosion protection properties of the conversion layers or are not sufficiently stable to use them in a continuous process or both.
Die Aufgabe der vorliegenden Erfindung bestand darin, die Nachteile der im Stand der Technik bekannten Mittel zur Herstellung von Korrosionsschutzschichten bzw. Konversionsschichten auf Metalloberflächen, insbesondere Oberflächen von Zink, Aluminium, Magnesium oder deren Legierungen, zu überwinden, wobei die Mittel frei von Chrom und Kobalt sein sollen.The object of the present invention was to overcome the disadvantages of the known in the prior art means for producing anticorrosive layers or conversion layers on metal surfaces, in particular surfaces of zinc, aluminum, magnesium or their alloys, wherein the means free of chromium and cobalt should be.
Gelöst wird diese Aufgabe durch ein Mittel zur Herstellung von Korrosionsschutzschichten auf Metalloberflächen, hergestellt durch die folgenden Stufen:
- A) Herstellen einer wässrigen Lösung, die wenigstens folgendes enthält:
- a) Oxo-Kationen VO<2+>,
- b) Halogen-Komplexanionen der Struktur MXa<b->, wobei M unter B, Ti, Zr, Si, Al ausgewählt ist, X unter F, Cl, Br, I ausgewählt ist, a eine ganze Zahl von 3 bis 6 ist und b eine ganze Zahl von 1 bis 4 ist,
- B) Bildung von Nanopartikeln mit einem mittleren Teilchendurchmesser < 500 nm in der Lösung in situ durch physikalische und/oder chemische Behandlung der Lösung, wobei die physikalische und/oder chemische Behandlung ausgewählt ist unter Veränderung der Temperatur, Veränderung der Ionen-Konzentration, Veränderung des pH-Wertes, Veränderung des Drucks, Übersättigung der Lösung, Rühren der Lösung, Zugabe eines Oxidationsmittels und/oder Zugabe eines Reduktionsmittels.
- A) preparing an aqueous solution containing at least:
- a) oxo cations VO <2+>,
- b) halogen complex anions of the structure MXa <b->, wherein M is selected from B, Ti, Zr, Si, Al, X is selected from F, Cl, Br, I, a is an integer from 3 to 6, and b is an integer from 1 to 4,
- B) formation of nanoparticles with an average particle diameter <500 nm in the solution in situ by physical and / or chemical treatment of the solution, wherein the physical and / or chemical treatment is selected by changing the temperature, changing the ion concentration, changing the pH, change in pressure, supersaturation of the solution, stirring of the solution, addition of an oxidizing agent and / or addition of a reducing agent.
Das erfindungsgemäße Mittel zeichnet sich unter anderem dadurch aus, daß es in situ erzeugte Nanopartikel enthält, die stabil oder wenigstens metastabil sind. Bei der Behandlung von Metalloberflächen mit dem erfindungsgemäßen Mittel wird eine Konversionsschicht bzw. Passivierungsschicht gebildet. Die in der Behandlungslösung in situ erzeugten Nanopartikel werden bei der Bildung der Konversionsschicht in diese eingebaut und bewirken dadurch eine besonders hohe Korrosionsschutzwirkung der behandelten Metalloberflächen. Bei dem erfindungsgemä-ßen Mittel werden diese Nanopartikel in situ durch Hydrolyse oder Oxidation der in der Ausgangslösung enthaltenen Stoffe erzeugt. Die Nanopartikel werden der Lösung nicht als bereits vorhandene nanopartikuläre Teilchen von außen zugesetzt. Es hat sich überraschenderweise gezeigt, daß die erfindungsgemäß in situ erzeugten Nanopartikel besser in die Konversionsschichten eingebaut werden und hierdurch diese Schichten dichter und somit korrosionsbeständiger werden als solche, die durch Aufbringen einer Korrosionsschutzlösung herstellbar sind, der Nanopartikel von außen zugegeben wurden, beispielsweise in Form einer Silica- oder Silikatlösung.The agent according to the invention is characterized inter alia by containing in situ generated nanoparticles which are stable or at least metastable. In the treatment of metal surfaces with the agent according to the invention, a conversion layer or passivation layer is formed. The nanoparticles generated in situ in the treatment solution are incorporated into the conversion layer during the formation of the conversion layer, thereby resulting in a particularly high corrosion protection effect of the treated metal surfaces. In the agent according to the invention, these nanoparticles are generated in situ by hydrolysis or oxidation of the substances contained in the starting solution. The nanoparticles are not added to the solution as already existing nanoparticulate particles from outside. It has surprisingly been found that the inventively generated in situ nanoparticles are better incorporated into the conversion layers and thereby these layers are denser and thus more corrosion resistant than those which can be produced by applying a corrosion protection solution were added to the nanoparticles from the outside, for example in the form of a Silica or silicate solution.
Die Nanopartikel in dem erfindungsgemäßen Mittel werden in situ durch physikalische und/oder chemische Behandlung der Ausgangslösung erzeugt, wobei eine kolloide Lösung entsteht. Mittels einer Tyndall-Lampe läßt sich die Bildung der Nanopartikel leicht nachweisen. Die Nanopartikel haben einen mittleren Teilchendurchmesser < 500 nm.The nanoparticles in the agent according to the invention are carried out in situ produces physical and / or chemical treatment of the starting solution, resulting in a colloidal solution. By means of a Tyndall lamp, the formation of nanoparticles can be easily detected. The nanoparticles have an average particle diameter <500 nm.
Die Nanopartikel entstehen aus den Halogen-Komplexanionen und/oder Oxo-Kationen durch Hydrolyse oder Oxidation. Die Nanopartikel bestehen somit im wesentlichen aus den Oxiden der Metalle oder Metalloide.The nanoparticles are formed from the halogen complex anions and / or oxo cations by hydrolysis or oxidation. The nanoparticles thus consist essentially of the oxides of the metals or metalloids.
Ohne daß sich die Anmelderin hiermit an eine Theorie bindet, wird angenommen, daß die Bildung von Nanopartikeln in situ durch die physikalische und/oder chemische Behandlung dadurch erfolgt, daß man den zunächst vorliegenden Gleichgewichtszustand der Ausgangslösung in einen Ungleichgewichtszustand überführt und das System sich in einem metastabilen Zustand stabilisiert. Die Überführung aus dem Gleichgewichtszustand in einen Ungleichgewichtszustand kann durch Veränderung der Temperatur, Veränderung der Ionen-Konzentration, Veränderung des pH-Wertes, Veränderung des Drucks, Übersättigung der Lösung, Rühren der Lösung, Zugabe eines Oxidationsmittels und/oder Zugabe eines Reduktionsmittels erfolgen. In einer bevorzugten Ausführungsform der Erfindung erfolgt die Bildung der Nanopartikel in situ durch Übersättigung der Lösung und/oder Rühren der Lösung.Without the applicant hereby binding to a theory, it is assumed that the formation of nanoparticles in situ by the physical and / or chemical treatment is carried out by bringing the initially present equilibrium state of the starting solution in an imbalance state and the system in a stabilized metastable state. The transition from the equilibrium state to an imbalance state can be effected by changing the temperature, changing the ion concentration, changing the pH, changing the pressure, supersaturating the solution, stirring the solution, adding an oxidizing agent and / or adding a reducing agent. In a preferred embodiment of the invention, the formation of the nanoparticles takes place in situ by supersaturation of the solution and / or stirring of the solution.
Das erfindungsgemäße Mittel kann in verschiedenen Formen und Fertigstellungsstufen vor der Behandlung von Metalloberflächen als Handelsprodukt bereitgestellt werden. Vorzugsweise wird das erfindungsgemäße Mittel als ein Konzentrat bereitgestellt, das vor der Verwendung noch zu verdünnen ist. Als Handelsprodukt geeignet ist das erfindungsgemäße Mittel, sobald die Oxo-Kationen und Halogen-Komplexanionen enthaltende wäßrige Lösung gemäß Stufe A) hergestellt und die Nanopartikel gemäß B) in situ gebildet sind.The composition of the invention may be provided in various forms and stages of completion prior to the treatment of metal surfaces as a commercial product. Preferably, the agent of the invention is provided as a concentrate which is to be diluted before use. The product according to the invention is suitable as a commercial product as soon as the aqueous solution containing oxo-cations and halogen complex anions has been prepared according to step A) and the nanoparticles according to B) have been formed in situ.
In einer bevorzugten Ausführungsform der Erfindung wird in einer weiteren Stufe C) der gemäß B) hergestellten Lösung eine oxidative Substanz zugegeben, ausgewählt unter Wasserstoffperoxid, organischen Peroxiden, Alkalimetallperoxiden, Persulfaten, Perboraten, Nitraten und Gemischen davon, wobei die Zugabe von Wasserstoffperoxid als oxidative Substanz besonders bevorzugt ist. Die Zugabe der oxidativen Substanz erfolgt zweckmäßigerweise vor der Verwendung des erfindungsgemäßen Mittels zur Herstellung von Korrosionsschutzschichten, wobei das erfindungsgemäße Mittel bereits mit der darin enthaltenen oxidativen Substanz bereitgestellt werden kann oder die oxidative Substanz erst kurz vor der Verwendung des erfindungsgemäßen Mittels beim Hersteller der Korrosionsschutzschichten zugegeben wird.In a preferred embodiment of the invention, in a further stage C) of the solution prepared according to B) an oxidative substance is added selected from hydrogen peroxide, organic peroxides, alkali metal peroxides, persulfates, perborates, nitrates and mixtures thereof, the addition of hydrogen peroxide as oxidative substance is particularly preferred. The addition of the oxidative substance is expediently carried out before the use of the agent according to the invention for the production of anticorrosion coatings, wherein the agent according to the invention can already be provided with the oxidative substance contained therein or the oxidative substance is added shortly before the use of the agent according to the invention at the manufacturer of the anticorrosive coatings ,
Die Zugabe der oxidativen Substanz vor der Verwendung des erfindungsgemäßen Mittels zur Herstellung von Korrosionsschutzschichten bewirkt u.a. eine Vorpassivierung der metallischen Oberfläche, insbesondere einer Zink- oder Zinklegierungsoberfläche, was vorteilhaft ist, da die Behandlungslösung äußerst aggressiv gegen die metallische Oberfläche sein kann und diese wenigstens teilweise auflösen könnte.The addition of the oxidative substance before the use of the agent according to the invention for the production of anticorrosive coatings causes, inter alia, a pre-passivation of the metallic surface, in particular a zinc or zinc alloy surface, which is advantageous because the treatment solution can be extremely aggressive against the metallic surface and dissolve it at least partially could.
In einer weiteren bevorzugten Ausführungsform des erfindungsgemäßen Mittels wird in einer weiteren Stufe D) der pH-Wert mittels einer Säure oder Base auf einen Wert im Bereich von 0,5 bis 5,0, vorzugsweise im Bereich von 1,0 bis 3,0, besonders bevorzugt im Bereich von 1,3 bis 2,0 eingestellt. Dies ist besonders vorteilhaft, wenn das erfindungsgemäße Mittel zur Herstellung von Korrosionsschutzschichten auf Zink- oder Zinklegierungsoberflächen verwendet wird. Die Einstellung des erfindungsgemäß bevorzugten sauren pH-Wertes gewährleistet einen ausreichenden Abtrag des metallischen Untergrundes, so daß die Metalloberfläche im wesentlichen vollständig von anhaftenden Verunreinigungen befreit wird und sich die Korrosionsschutzschicht anschließend vollständig und lückenlos über die gesamte Oberfläche ausbilden kann.In a further preferred embodiment of the agent according to the invention, in a further stage D) the pH is adjusted by means of an acid or base to a value in the range from 0.5 to 5.0, preferably in the range from 1.0 to 3.0, more preferably adjusted in the range of 1.3 to 2.0. This is particularly advantageous when the composition according to the invention is used for the production of anticorrosive coatings on zinc or zinc alloy surfaces. The setting of the invention preferred acidic pH ensures sufficient removal of the metallic substrate, so that the metal surface is substantially completely freed of adhering impurities and the corrosion protection layer can then form completely and completely over the entire surface.
In einer weitere bevorzugten Ausführungsform der Erfindung wird das erfindungsgemäße Mittel hergestellt, indem die Bildung von Nanopartikeln gemäß Stufe B) bei einer Temperatur im Bereich von Raumtemperatur bis 100 °C, vorzugsweise im Bereich von 30 °C bis 80 °C, besonders bevorzugt im Bereich von 35 °C bis 50 °C durchgeführt wird. Bei einer zu niedrigen Temperatur erfolgt die Bildung von Nanopartikeln in einer unwirtschaftlich langsamen Geschwindigkeit. Darüber hinaus besteht die Gefahr, daß sich die Teilchen zusammenlagern und der nanopartikuläre Charakter verloren geht. Eine zu hohe Temperatur hat den Nachteil, daß der metastabile Zustand nicht erreicht wird und keine Nanopartikel gebildet werden.In a further preferred embodiment of the invention, the agent according to the invention is prepared by the formation of nanoparticles according to step B) at a temperature in the range of room temperature to 100 ° C, preferably in the range of 30 ° C to 80 ° C, more preferably in the range from 35 ° C to 50 ° C is performed. At too low a temperature, nanoparticles are formed at an uneconomically slow rate. In addition, there is a risk that the particles accumulate and the nanoparticulate character is lost. Too high a temperature has the disadvantage that the metastable state is not reached and no nanoparticles are formed.
In einer weiteren bevorzugten Ausführungsform der Erfindung wird das Mittel hergestellt, indem die Halogen-Komplexanionen b) der wäßrigen Lösung in Stufe A) in der Form ihrer Metallsalze, vorzugsweise ihrer Alkalimetallsalze, besonders bevorzugt ihrer Natrium- und Kaliumsalze zugegeben werden. Ganz besonders bevorzugt ist die Zugabe der Feststoffe, indem man zunächst eine wäßrige Lösung der Oxo-Kationen a) bereitstellt und den die Halogen-Komplexanionen enthaltenden Feststoff zugibt und löst.In a further preferred embodiment of the invention, the agent is prepared by adding the halogen complex anions b) to the aqueous solution in step A) in the form of their metal salts, preferably their alkali metal salts, more preferably their sodium and potassium salts. Very particular preference is given to the addition of the solids by initially preparing an aqueous solution of the oxo cations a) and adding and dissolving the solid containing the halogen complex anions.
Erfindungsgemäß ganz besonders bevorzugt sind die Halogen-Komplexanionen b) Fluoroanionen, die unter BF4<1->, TiF6<2->, ZrF6<2->, SiF6<2->, AIF6<3-> und Gemischen davon ausgewählt sind.Very particular preference according to the invention is given to the halogen complex anions b) fluoroanions selected from BF4 <1->, TiF6 <2->, ZrF6 <2->, SiF6 <2->, AIF6 <3-> and mixtures thereof.
In einer weiteren erfindungsgemäß bevorzugten Ausführungsform werden der wäßrigen Lösung in Stufe A) weitere Metallsalze zugegeben, vorzugsweise Salze der Metalle B, Ti, Zr, Si und/oder Al. Vorzugsweise werden die Metalle in der Form der Metallhalogenide, Metallnitrate und/oder Metallsulfate zugegeben. Hierdurch kann die farbliche Gestaltung der Schutzschicht verändert und/oder der Korrosionsschutz erhöht werden.In a further preferred embodiment according to the invention, further metal salts are added to the aqueous solution in stage A), preferably salts of the metals B, Ti, Zr, Si and / or Al. Preferably, the metals are added in the form of the metal halides, metal nitrates and / or metal sulfates. As a result, the color design of the protective layer can be changed and / or the corrosion protection can be increased.
In einer weiteren bevorzugten Ausführungsform der Erfindung enthält die in Stufe A) hergestellte wäßrige Lösung die Oxo-Kationen in einer Konzentration von 0,1 bis 0,5 Gew.-%, vorzugsweise in einer Konzentration von 0,1 bis 0,3 Gew.-%.In a further preferred embodiment of the invention, the aqueous solution prepared in step A) contains the oxo cations in a concentration of 0.1 to 0.5 wt .-%, preferably in a concentration of 0.1 to 0.3 wt. -%.
In einer weiteren bevorzugten Ausführungsform der Erfindung enthält die in der Stufe A) hergestellte wäßrige Lösung die Halogen-Komplexanionen in einer Konzentration von 0,1 bis 3,0 Gew.-%, vorzugsweise in einer Konzentration von 0,5 bis 2,0 Gew.-%.In a further preferred embodiment of the invention, the aqueous solution prepared in step A) contains the halogen complex anions in a concentration of 0.1 to 3.0 wt .-%, preferably in a concentration of 0.5 to 2.0% by weight.
Wie oben bereits ausgeführt wurde, kann das erfindungsgemäße Mittel als ein Konzentrat bereitgestellt werden, das vor der Anwendung zu verdünnen ist. Alternativ kann das erfindungsgemäße Mittel bereits in der für die Anwendung geeigneten Konzentration bzw. Verdünnung bereitgestellt werden. In diesem Fall wird die in Stufe B) erhaltene Lösung zweckmäßigerweise vor oder nach der Zugabe einer oxidativen Substanz in Stufe C) mit Wasser in einem Verhältnis von 1:3 bis 1:5 verdünnt.As stated above, the agent of the invention may be provided as a concentrate to be diluted before use. Alternatively, the agent according to the invention can already be provided in the concentration or dilution suitable for the application. In this case, the solution obtained in step B) is expediently diluted with water in a ratio of 1: 3 to 1: 5 before or after the addition of an oxidative substance in step C).
Die Anwendung des erfindungsgemäßen Mittels zur Herstellung von Korrosionsschutzschichten erfolgt durch direkte Behandlung der Metalloberflächen mit dem Mittel, vorzugsweise durch Eintauchen oder Schwenken der Gegenstände mit Metalloberflächen in das bzw. dem Mittel. Die Anwendung durch Eintauchen oder Schwenken erfolgt vorzugsweise bei einer Temperatur des Behandlungsbades im Bereich von 20 bis 100°C, vorzugsweise von 30 bis 70°C, bevorzugter von 40 bis 60°C und besonders bevorzugt bei etwa 50°C.The application of the composition according to the invention for the production of anticorrosive coatings is carried out by direct treatment of the metal surfaces with the agent, preferably by immersing or pivoting the objects with metal surfaces in the or the agent. Application by dipping or panning is preferably carried out at a temperature of the treatment bath in the range of 20 to 100 ° C, preferably 30 to 70 ° C, more preferably 40 to 60 ° C, and most preferably about 50 ° C.
Die geeignetste Behandlungsdauer zur Herstellung von Korrosionsschutzschichten durch Eintauchen oder Schwenken der Gegenstände mit Metalloberflächen in das bzw. dem Behandlungsbad variiert in Abhängigkeit von verschiedenen Parametern, wie z. B. der Zusammensetzung der Behandlungslösung, der Behandlungstemperatur, der Art der Metalloberfläche und dem Grad des gewünschten Korrosionsschutzes. Bei Metalloberflächen aus Zink oder Zinklegierung liegt eine geeignete Behandlungsdauer im Bereich von 10 bis 120 Sekunden, vorzugsweise im Bereich von 20 bis 60 Sekunden.The most suitable treatment time for the production of anticorrosive coatings by immersing or pivoting the objects with metal surfaces in the treatment or the treatment varies depending on various parameters, such as. As the composition of the treatment solution, the treatment temperature, the type of metal surface and the degree of corrosion protection desired. For metal surfaces of zinc or zinc alloy, a suitable treatment time is in the range of 10 to 120 seconds, preferably in the range of 20 to 60 seconds.
Weitere Vorteile, Merkmale und Ausführungsformen der vorliegenden Erfindung werden anhand der nachfolgenden Beispiele deutlich.Further advantages, features and embodiments of the present invention will become apparent from the following examples.
Zur Herstellung erfindungsgemäßer Mittel und von Vergleichszusammensetzungen wird eine wäßrige Lösung von Oxo-Anionen a) hergestellt. Unter leichtem Rühren wird anschließend die Halogen-Komplexanionen-Komponente b), in diesem Beispiel eine Fluoroanionen-Komponente, als Feststoff in 800 ml der zuvor hergestellten Lösung gelöst. Anschließend wird diese Lösung einer physikalischen und/oder chemischen Behandlung durch starkes Rühren (Propellerrührer, 700 bis 1000 Upm) unterzogen. Die Bildung von Nanopartikeln wird mittels einer Tyndall-Lampe überprüft. Anschließend wird die erhaltene Lösung mit Wasser auf 1 I aufgefüllt.For the preparation of compositions according to the invention and comparative compositions, an aqueous solution of oxo anions a) is prepared. With gentle stirring, the halogen complex anion component b), in this example a fluoroanion component, is then dissolved as a solid in 800 ml of the previously prepared solution. Subsequently, this solution is subjected to physical and / or chemical treatment by vigorous stirring (propeller stirrer, 700 to 1000 rpm). The formation of nanoparticles is checked by means of a Tyndall lamp. Subsequently, the solution obtained is made up to 1 l with water.
Die zuvor hergestellte Lösung wird vor der Verwendung zur Herstellung von Korrosionsschutzschichten im Verhältnis 1 zu 4 mit Wasser verdünnt (1 I Lösung plus 3 I Wasser). Anschließend wird 1 Liter 10 %-ige H2O2-Lösung hinzugefügt und der pH-Wert mit NaOH oder HNO3 auf einen Wert von 1,5 bis 1,8 eingestellt. Die einzelnen Komponenten der hergestellten Lösungen (5 Liter Lösung je Ansatz) und die physikalischen und/oder chemischen Behandlungen sind in der nachfolgenden Tabelle 1 wiedergegeben.
Tabelle 1 zeigt, daß ohne Behandlung der Lösungen durch Rühren (Lösungen 1b bis 11b) kein Tyndall-Effekt beobachtet und somit keine Bildung von Nanopartikeln erzielt wurde. Das gleiche wurde beobachtet, wenn die Fluoroanionen-Komponente in der Form ihrer freien Säure mit und ohne Rühren verwendet wurde (Lösungen 2a, 2b, 4a, 4b, 7a, 7b, 9a, 9b, 11a und 11b).Table 1 shows that without treatment of the solutions by stirring (solutions 1b to 11b) no Tyndall effect was observed and thus no formation of nanoparticles was achieved. The same was observed when the fluoroanion component was used in the form of its free acid with and without stirring (solutions 2a, 2b, 4a, 4b, 7a, 7b, 9a, 9b, 11a and 11b).
Galvanisch verzinkte Bleche wurden mit den zuvor hergestellten und in Tabelle 1 angegebenen Behandlungslösungen durch Eintauchen in die Lösungen für 60 Sekunden bei 50°C behandelt. Anschließend wurden die Bleche mit Wasser gespült und einem Korrosionstest nach DIN 50021 SS (Salzsprühtest) für Trommelware unterzogen und die Dauer bis zum Auftreten von i) ersten Korrosionserscheinungen und ii) 5% Weißrost verglichen. Die Ergebnisse sind in Tabelle 2 wiedergegeben.
Claims (11)
- Composition for producing anti-corrosion layers on metal surfaces, which is produced by the following steps:A) producing an aqueous solution which comprises at least the following:a) oxo cations VO<2+>,b) halogen complex anions of the structure MXa<b->, where M is selected from B, Ti, Zr, Si and Al, X is selected from F, Cl, Br and I, a is an integer from 3 to 6 and b is an integer from 1 to 4,B) forming nanoparticles having a mean particle diameter < 500 nm in the solution in situ by physical and/or chemical treatment of the solution, where the physical and/or chemical treatment is selected from change in the temperature, change in the ion concentration, change in the pH, change in the pressure, supersaturating the solution, agitating the solution, adding an oxidizing agent and/or adding a reducing agent.
- Composition according to Claim 1, characterized by the further step in whichC) there is added, to the solution produced in accordance with step B), an oxidative substance selected from hydrogen peroxide, organic peroxides, alkali metal peroxides, persulfates, perborates, nitrates and mixtures thereof.
- Composition according to Claim 2, characterized by the further step in whichD) the pH of the solution produced in accordance with step C) is adjusted by means of an acid or a base to a value in the range from 0.5 to 5.0, preferably in the range from 1.0 to 3.0, particularly preferably in the range from 1.3 to 2.0.
- Composition according to any of Claims 1 to 3, characterized in that the formation of nanoparticles in accordance with step B) is accomplished by supersaturating the solution with halogen complex anions b) and/or by agitating the solution.
- Composition according to any of Claims 1 to 4, characterized in that the formation of nanoparticles in accordance with step B) is carried out at a temperature in the range from room temperature to 100°C, preferably in the range from 30°C to 80°C, particularly preferably in the range from 35°C to 50°C.
- Composition according to any of Claims 1 to 5, characterized in that the halogen complex anions b) are added to the aqueous solution in step A) in the form of their metal salts, preferably their alkali metal salts, particularly preferably their sodium and potassium salts.
- Composition according to any of Claims 1 to 6, characterized in that there are added, to the aqueous solution in step A), further metal salts, preferably salts of the metals B, Ti, Zr, Si and/or Al, and preferably in the form of the metal halides, metal nitrates and/or metal sulfates.
- Composition according to any of Claims 1 to 7, characterized in that the aqueous solution produced in step A) comprises the oxo cations in a concentration of 0.1 to 0.5% by weight, preferably in a concentration of 0.1 to 0.3% by weight.
- Composition according to any of Claims 1 to 8, characterized in that the aqueous solution produced in step A) comprises the halogen complex anions in a concentration of 0.1 to 3.0% by weight, preferably in a concentration of 0.5 to 2.0% by weight.
- Composition according to any of Claims 2 to 9, characterized in that the solution obtained in step B) is diluted with water in a ratio from 1:3 to 1:5 prior to the addition of an oxidative substance in step C).
- Composition according to any of Claims 1 to 10, characterized in that the halogen complex anions b) are selected from BF4<1->, TiF6<2->, ZrF6<2->, SiF6<2->, AlF6<3-> and mixtures thereof.
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ES07105237T ES2388302T5 (en) | 2007-03-29 | 2007-03-29 | Agents for manufacturing corrosion protection layers on metal surfaces |
EP07105237.7A EP1978131B2 (en) | 2007-03-29 | 2007-03-29 | Means for manufacturing corrosion protection coats on metal surfaces |
JP2010500230A JP5279811B2 (en) | 2007-03-29 | 2008-03-20 | Agent that forms an anti-corrosion layer on metal surfaces |
CN2008800104018A CN101668881B (en) | 2007-03-29 | 2008-03-20 | Agent for the production of anticorrosive layers on metal surfaces |
US12/593,632 US8764916B2 (en) | 2007-03-29 | 2008-03-20 | Agent for the production of anti-corrosion layers on metal surfaces |
PCT/EP2008/053346 WO2008119675A1 (en) | 2007-03-29 | 2008-03-20 | Agent for the production of anticorrosive layers on metal surfaces |
KR1020097020409A KR101493458B1 (en) | 2007-03-29 | 2008-03-20 | Agent for the production of anti-corrosion layers on metal surfaces |
BRPI0809299-0A2A BRPI0809299A2 (en) | 2007-03-29 | 2008-03-20 | AGENT FOR PRODUCTION OF ANTI-CORROSION LAYERS ON METAL SURFACES |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP07105237.7A EP1978131B2 (en) | 2007-03-29 | 2007-03-29 | Means for manufacturing corrosion protection coats on metal surfaces |
Publications (3)
Publication Number | Publication Date |
---|---|
EP1978131A1 EP1978131A1 (en) | 2008-10-08 |
EP1978131B1 EP1978131B1 (en) | 2012-06-06 |
EP1978131B2 true EP1978131B2 (en) | 2019-03-06 |
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Application Number | Title | Priority Date | Filing Date |
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EP07105237.7A Active EP1978131B2 (en) | 2007-03-29 | 2007-03-29 | Means for manufacturing corrosion protection coats on metal surfaces |
Country Status (8)
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US (1) | US8764916B2 (en) |
EP (1) | EP1978131B2 (en) |
JP (1) | JP5279811B2 (en) |
KR (1) | KR101493458B1 (en) |
CN (1) | CN101668881B (en) |
BR (1) | BRPI0809299A2 (en) |
ES (1) | ES2388302T5 (en) |
WO (1) | WO2008119675A1 (en) |
Families Citing this family (11)
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JP2009209407A (en) * | 2008-03-04 | 2009-09-17 | Mazda Motor Corp | Agent for chemical conversion treatment and surface-treated metal |
EP2309027B1 (en) | 2009-09-23 | 2011-09-21 | ATOTECH Deutschland GmbH | Treatment solution for generating chrome and cobalt-free black conversion coatings |
ES2924127T3 (en) | 2012-08-29 | 2022-10-04 | Ppg Ind Ohio Inc | Lithium-containing zirconium pretreatment compositions, associated methods for treating metal substrates, and related coated metal substrates |
BR112015004358B1 (en) | 2012-08-29 | 2021-05-25 | Ppg Industries Ohio, Inc | method for coating a metal substrate and pretreatment composition for treating a metal substrate |
US20160068957A1 (en) * | 2013-04-12 | 2016-03-10 | Haydn N.G. Wadley | Corrosion resistant metal and metal alloy coatings containing supersaturated concentrations of corrosion inhibiting elements and methods and systems for making the same |
CN103205739B (en) * | 2013-04-28 | 2015-04-08 | 东南大学 | Surface chemical treatment method for improving abrasive resistance of steel material |
DE102013107506A1 (en) | 2013-07-16 | 2015-01-22 | Thyssenkrupp Rasselstein Gmbh | Method for passivation of band-shaped black plate |
DE102015113878B4 (en) | 2015-08-21 | 2023-03-16 | Thyssenkrupp Ag | Process for the thermal treatment of a black plate coated with a conversion layer |
WO2018006270A1 (en) * | 2016-07-05 | 2018-01-11 | 深圳市恒兆智科技有限公司 | Chromium-free aluminum conversion coating agent, aluminum material, and surface conversion coating treatment method |
KR20190043155A (en) | 2016-08-24 | 2019-04-25 | 피피지 인더스트리즈 오하이오 인코포레이티드 | Alkaline compositions for treating metal substrates |
US11008254B2 (en) | 2019-08-08 | 2021-05-18 | Specialty Granules Investments Llc | Building materials comprising agglomerated particles |
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EP1950325A2 (en) † | 2007-01-19 | 2008-07-30 | Nihon Hyomen Kagaku Kabushiki Kaisha | Chromium-free solution for treating metal surfaces |
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IN176027B (en) * | 1988-08-12 | 1995-12-23 | Alcan Int Ltd | |
JP2870170B2 (en) * | 1990-09-21 | 1999-03-10 | 日本板硝子株式会社 | Method for producing titanium oxide coating |
US6193815B1 (en) * | 1995-06-30 | 2001-02-27 | Henkel Corporation | Composition and process for treating the surface of aluminiferous metals |
DE10010758A1 (en) * | 2000-03-04 | 2001-09-06 | Henkel Kgaa | Corrosion protection of zinc, aluminum and/or magnesium surfaces such as motor vehicle bodies, comprises passivation using complex fluorides of Ti, Zr, Hf, Si and/or B and organic polymers |
CA2408675A1 (en) * | 2000-05-11 | 2001-11-15 | Henkel Corporation | Metal surface treatment agent |
JP3851106B2 (en) * | 2000-05-11 | 2006-11-29 | 日本パーカライジング株式会社 | Metal surface treatment agent, metal surface treatment method and surface treatment metal material |
US6524403B1 (en) * | 2001-08-23 | 2003-02-25 | Ian Bartlett | Non-chrome passivation process for zinc and zinc alloys |
JP4167046B2 (en) * | 2002-11-29 | 2008-10-15 | 日本パーカライジング株式会社 | Metal surface treatment agent, metal surface treatment method and surface treatment metal material |
JP4205939B2 (en) * | 2002-12-13 | 2009-01-07 | 日本パーカライジング株式会社 | Metal surface treatment method |
JP4402991B2 (en) * | 2004-03-18 | 2010-01-20 | 日本パーカライジング株式会社 | Metal surface treatment composition, metal surface treatment liquid, metal surface treatment method and metal material |
-
2007
- 2007-03-29 EP EP07105237.7A patent/EP1978131B2/en active Active
- 2007-03-29 ES ES07105237T patent/ES2388302T5/en active Active
-
2008
- 2008-03-20 BR BRPI0809299-0A2A patent/BRPI0809299A2/en not_active IP Right Cessation
- 2008-03-20 US US12/593,632 patent/US8764916B2/en active Active
- 2008-03-20 JP JP2010500230A patent/JP5279811B2/en active Active
- 2008-03-20 KR KR1020097020409A patent/KR101493458B1/en active IP Right Grant
- 2008-03-20 WO PCT/EP2008/053346 patent/WO2008119675A1/en active Application Filing
- 2008-03-20 CN CN2008800104018A patent/CN101668881B/en active Active
Patent Citations (3)
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US5743971A (en) † | 1995-08-21 | 1998-04-28 | Dipsol Chemicals Co., Ltd. | Liquid rust proof film-forming composition and rust proof film-forming method |
US20030205299A1 (en) † | 2002-04-29 | 2003-11-06 | Greene Jeffrey Allen | Conversion coatings including alkaline earth metal fluoride complexes |
EP1950325A2 (en) † | 2007-01-19 | 2008-07-30 | Nihon Hyomen Kagaku Kabushiki Kaisha | Chromium-free solution for treating metal surfaces |
Also Published As
Publication number | Publication date |
---|---|
KR101493458B1 (en) | 2015-02-13 |
CN101668881A (en) | 2010-03-10 |
EP1978131B1 (en) | 2012-06-06 |
ES2388302T3 (en) | 2012-10-11 |
KR20100014685A (en) | 2010-02-10 |
US20100126633A1 (en) | 2010-05-27 |
BRPI0809299A2 (en) | 2014-10-14 |
WO2008119675A1 (en) | 2008-10-09 |
EP1978131A1 (en) | 2008-10-08 |
JP2010532816A (en) | 2010-10-14 |
JP5279811B2 (en) | 2013-09-04 |
CN101668881B (en) | 2011-08-24 |
US8764916B2 (en) | 2014-07-01 |
ES2388302T5 (en) | 2019-10-18 |
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