WO2016107791A1 - Passivierungszusammensetzung aufweisend eine silanmodifizierte silikatverbindung - Google Patents
Passivierungszusammensetzung aufweisend eine silanmodifizierte silikatverbindung Download PDFInfo
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- WO2016107791A1 WO2016107791A1 PCT/EP2015/080979 EP2015080979W WO2016107791A1 WO 2016107791 A1 WO2016107791 A1 WO 2016107791A1 EP 2015080979 W EP2015080979 W EP 2015080979W WO 2016107791 A1 WO2016107791 A1 WO 2016107791A1
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- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/32—Alkali metal silicates
- C01B33/325—After-treatment, e.g. purification or stabilisation of solutions, granulation; Dissolution; Obtaining solid silicate, e.g. from a solution by spray-drying, flashing off water or adding a coagulant
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- 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
- B05D7/16—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 using synthetic lacquers or varnishes
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- 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
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- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
- C23C22/42—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also phosphates
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- 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
- C23C22/46—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 oxalates
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- 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
- C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/53—Treatment of zinc or alloys based thereon
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- 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
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- 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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
Definitions
- the invention relates to a passivation composition containing silane-modified silicate compounds and to a method for producing a silane-modified silicate and a metallic substrate coated with this passivation composition.
- silane-modified silicate compounds are more suitable for anticorrosive coatings than a mixture of the individual silanes and silicates.
- Silane-modified silicate compounds obtained by alkaline hydrolysis of the monomeric silane in silicate solutions z. B. in water glasses are - as taught in EP 2 216 371 A1, applied in the alkaline range.
- Acid coatings containing colloidal silica particles are obtained by acid hydrolysis of silanes in acidic silica sols.
- the passivation composition according to the invention for a metallic substrate comprising a silane-modified silicate compound in an acidic aqueous solution in the alkaline pH range is obtainable by at least partial hydrolysis and / or condensation of at least one silane in the presence of at least one silicate at a pH equal to or greater 8, and then adjusting a pH equal to or less than 7 by adding acid.
- the method for producing a silane-modified silicate is carried out with the steps comprising at least partially hydrolyzing a silane in the presence of a silicate compound and at least partially condensing the hydrolyzed silane with the silicate at a pH equal to or greater than 8 to a silane-modified silicate and then adjusting a pH equal to or less than 7 by adding acid.
- silane-modified silicate compounds have an excellent anticorrosive effect.
- the silane or siloxane is bound to the silicate by hydrolysis and / or condensation in an alkaline medium as a covalent side chain.
- hydrolysis and condensation are also used individually in connection with the description of this invention, they respectively designate all reactions taking place in the preparation of the silane-modified silicate compound.
- the anticorrosive effect does not fully develop when the passivation composition with these alkali-hydrolyzed silane-modified silicate compounds is also applied to the metallic substrate at an alkaline pH.
- water glasses which are hydrolyzed or condensed in alkaline with a silane or siloxane or mixtures thereof can be acidified to a pH of 7 or less without precipitation of water glass. This is particularly evident when using lithium silicate or lithium polysilicate and when using a mixture of waterglasses containing lithium silicate or lithium polysilicate.
- the passivating composition containing the silane-modified silicate compound produced in the alkaline state by hydrolysis and / or condensation of the silane in admixture with acid may be at pH 7 or lower, typically at acidic pHs of at most pH 6 or up to pH 5 can be used as an effective corrosion protection coating. Acidification preferably sets a pH value between 2 and 4, which is reached and can be maintained without precipitation or flocculation of the silane-modified silicate compound.
- the acidic passivation composition according to the invention adopts the metal surface of the substrate, after which dissolved metal ions from the surface of the substrate are incorporated into the passivation .
- Such metal ions may be present in the passivation layer e.g. be detected by GD-OES (glow discharge - optical emission spectroscopy), z.
- GD-OES low discharge - optical emission spectroscopy
- zinc, iron and / or magnesium ions which are detectable in the form of zinc, iron and / or magnesium silicate.
- the heating of the metal surface of the substrate which is carried out by the acid of the passivation composition according to the invention, creates a chemically defined surface and may well be understood as an acidic cleaning step.
- the metal surface is leveled and the adhesion of the passivation layer is improved.
- the setting of a pH of 7 or less, ie an acidic pH, is carried out for the passivation composition according to the invention by adding acid to the aqueous alkaline solution which contains completely or partially hydrolyzed or condensed, silane-modified silicate compounds.
- the pH can be adjusted with inorganic or organic acids or with a mixture of acids.
- the pH after adding acid is preferably adjusted to a value between pH 2 and pH 5.
- Acids are preferably used for acidification, which contain phosphorus, such as. As diphosphoric acid, phosphonic acids or di-phosphonic acids or a mixture of these acids. It is advantageous z. B.
- inorganic acids such as nitric acid or sulfuric acid can be used, but also organic acids such as acetic acid, acrylic acid, oxalic acid, citric acid, fumaric acid, benzoic acid, succinic acid, maleic acid, salicylic acid, aminosalicylic acid, nicotinic acid, formic acid, malic acid, Tartaric acid, ascorbic acid, propionic acid, lactic acid, phthalic acid.
- the acidification takes place in coordination with the metallic substrate to an optimum pH for this substrate.
- lithium polysilicate is particularly preferred. If lithium polysilicate is used in aqueous solution for the preparation of a silane-modified silicate compound, an alkaline pH above pH 9 to pH 12 arises without further action, which is completely sufficient for partial or complete hydrolysis in the alkaline state. But water glasses such as sodium, NH 4 - and / or potassium silicate are suitable, both alone or in combination with each other, but especially to be used in a mixture with lithium polysilicate for the inventive method and for the preparation of the passivation composition according to the invention.
- silane-modified silicate compounds according to the invention which is used in the passivation composition
- an epoxide-functional, phenoxy-functional, vinyl-functional or amino-functional silane alkylalkoxysilanes, in this case mono-, di- or trialkylalkoxysilanes, are suitable, individually or as a mixture in combination with silicates, to build up a corrosion-protecting coating.
- silanes which have at least one Si-C bond, ie a bond between a silicon and a carbon atom.
- Various silanes can be used together in a mixture.
- silanes are methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and 3-mercaptopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2 Aminopropyl) -3-aminopropyltrimethoxysilane, N-cyclohexyl-3-aminopropyltrimethoxysilane, N-cyclohexylaminomethyltriethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminomethylamino) propyltriethoxysilane, N- (2-aminoethoxys
- the silane is used either singly or in admixture with other silanes.
- the silane is used as a monomer, but it can also be an oligomer, d. , Siloxane or a mixture of silane and siloxane in the presence of a silicate or a mixture of silicates can be hydrolyzed and / or condensed. If, in connection with this invention, silane-modified silicates are mentioned or described, the use of siloxane-modified silicates is therefore also always meant and covered.
- the silane-modified or siloxane-modified silicates can be detected by conventional analytical methods both in the aqueous passivation composition and as a dried coating on the metallic substrate, typically z.
- silane-modified silicates by hydrolysis or condensation in the alkaline pH range can, according to an alternative embodiment, also be carried out in such a way that oligomers or polymers are used which react via reactive Have organic side groups with each other crosslinked silanes.
- oligomers or polymers which are used for the modification of the silicates carry 1 to 3 reactive organic side groups, preferably only one reactive side group.
- these oligomers or polymers made up of silanes have other side groups, preferably alkoxy or silanol groups.
- the preferred side group reactive group is selected from the group comprising epoxy, amine, acrylate, isocyanate, alcohol, acid or ester groups.
- silicate is to be modified with an oligomer or polymer based on a silane, it is advisable first to prepare the oligomer or polymer by hydrolysis or condensation of the silanes and then alkaline hydrolysis or condensation to produce the silane-modified silicates in the presence of the silicate Lithium polysilicate to produce.
- silane-modified silicate in a second stage by further reaction with a tetraalkoxysilane, for.
- tet ramethoxysilane further modified.
- the further modification of the already silane-modified silicate is carried out to z. B. to achieve one or more of the following effects:
- the molecular weight is increased, the crosslinking density is increased and / or the reactivity is increased.
- the subsequent hydrolysis with a tetraalkoxysilane takes place under the same conditions as described here in connection with the first stage of the silane modification.
- Silane and silicate are used in aqueous solution in the following proportions: Silane or siloxane can be used in an amount of from 1% by weight to 99% by weight, based on the total amount of silicate and silane used for the hydrolysis and / or condensation. However, already show silane-modified silicate compounds containing only small amounts of silane, z. B. up to 20% by weight, a significantly improved corrosion protection. Silane-modified silicates in which the proportion of the silane is 20% by weight or more, preferably between 40% by weight and 60% by weight, are highly suitable. In the preparation of the silane-modified silicates, silane and silicate are each advantageously used in a weight ratio of from 0.1: 1 to 2.5: 1, preferably from 0.4 to 1: 1.
- the silane can be used as a single compound or as a mixture of Silanes are used, the same applies to the silicate, the use of lithium silicate is preferred, both individually and in a silicate mixture.
- the solids content of the passivation composition produced by the process according to the invention is between 1% and 70%.
- the solids content is advantageously between 1% and 50%, particularly advantageously between 2% and 40%.
- silane-modified or siloxane-modified silicates By the common hydrolysis and condensation of silicates and silanes or siloxanes in aqueous solution at a pH equal to or greater than 8 takes place on the one hand, the formation of silane-modified or siloxane-modified silicates.
- the hydrolysis may optionally be continued after acidification to a pH equal to or less than 7.
- alcohols which are liberated at the factory by alkaline and optionally acid hydrolysis can be removed so that aqueous acidic compositions can be provided which are low in volatile organic compounds (low in VOC) or free from volatile organic compounds (VOC-free).
- the liberated by the hydrolysis alcohols can, for example, by ultramembrane filtration or reverse osmosis, but also by distillation, for. B.
- Typical inventive aqueous alkaline or acidified compositions for passivating metallic substrates contain at most 1% by weight of alcohol, preferably at most 0.3% by weight of alcohol.
- the removal of the alcohol also promotes the hydrolysis or condensation reaction of the silane or of the silane with the silicate.
- the hydrolysis and condensation in the alkaline generally proceeds under the following conditions: The hydrolysis and condensation takes place at room temperature, by slow addition, usually over several hours, up to a maximum of 12 hours, of the silane or silane mixture to the silicate and with constant stirring. After completion of the addition is advantageously still stirred for some time.
- the implementation can take place over a period of 1 to 48 hours.
- Further stirring after completion of the hydrolysis or condensation is also carried out for at least 1 hour, but can, for. B. to improve the application properties and continue for up to 24 hours.
- the acidification is usually also at room temperature.
- the completely or partially hydrolyzed and / or condensed silicate-silane mixture, the acid or the acid mixture is added slowly with constant stirring; also the acidification can take 1 to 10 hours. It is constantly the pH is controlled and the addition ends when the desired pH is reached. Even after the acidification is still advantageous for some time for 1 to 24 hours further stirred to improve the application properties.
- the passivation composition has one or more titanate and / or zirconate compounds.
- the titanate and / or zirconate compound may be hydrolyzed or condensed with the silane, either in the presence of the silicate or previously in a reaction only between the silane and the titanate and / or zirconate compound. If the titanate and / or zirconate compound is completely or partially hydrolyzed or condensed in advance with the silane or siloxane, this can be achieved, for example, by Example, as disclosed in US 5,849,110. If the titanate and / or zirconate compound is added in the presence of the silicate, this can be done either already in the alkaline hydrolysis or only after the acidification.
- the titanate and / or zirconate compound is incorporated less into the silane-modified silicate skeleton the later it is added; The incorporation is therefore the lowest when the titanate and / or zirconate compound is added only after the acidification of the silane-modified silicate compound, especially if the hydrolysis or condensation is usually largely completed at this time. Nevertheless, even with the late addition of titanates or zirconates or of mixtures of titanates and / or zirconates, an improvement in the anticorrosive effect can be observed. Often then the titanate and / or zirconate is in the form of nanoparticles.
- titanate and / or zirconate compound is added to the silicate simultaneously with the silane, it is also possible to form a covalent bond between the titanate and / or zirconate compound and the silicate, comparable to the covalent bond between the silane and the silicate.
- a covalent bond to silane-bound silane groups is possible and is preferred within the scope of the invention.
- the resulting polymer thus has side chains in different amounts. in a simplified representation, the structural elements "water glass Si-O-Ti-R" or “water glass Si-O-Zr-R", wherein the same letters have the same meaning as stated above and wherein Ti for titanium and Zr for Zirconium stands.
- titanates and zirconates are monoalkyltrialkoxytitanate, Dialkyldialkoxytitanate, Trialkylmonoalkoxytitanate and Tetraalkoxytitanate such.
- the titanium compound, the zirconium compound or mixtures of titanium, zirconium or titanate and zirconium compounds is mixed with the silane at room temperature.
- the proportion of titanium and / or zirconium compounds, including titanates and / or zirconates, which are used individually or as a mixture, based on the total amount of silane and titanium and zirconium compounds, is between 0.01% by weight. % and 50% by weight.
- this mixture typically: silane, titanates, zirconates
- this mixture typically: silane, titanates, zirconates
- this mixture in lithium polysilicate or another silicate or a mixture of silicates is incorporated dropwise with stirring, stirred for some time and then acidified.
- the addition of the titanium or zirconium compound can be carried out after acidification at room temperature. This is also added dropwise with stirring and then stirred for a further 1 to 24 hours.
- the implementation of the method according to the invention with mixtures of silanes, silanes and titanates and / or zirconates, but also with mixtures of silicates, can be used inter alia for adjusting the crosslinking density of the passivation layer which is produced on the metallic substrate.
- the crosslinking density of the passivation layer and its strength, which are e.g. B. can be influenced by the solids content of the passivation composition, influence the corrosion property of the applied and dried on the metallic substrate passivation. A higher-networked film can also be used lower film thickness offer good corrosion protection.
- the adhesion of the passivation on the metallic substrate is improved, in particular by covalent bonding of the passivation to the OH groups of the surface of the metallic substrate.
- the improved adhesion to the surface of the metallic substrate may be assisted by the addition of titanates and / or zirconates.
- an acidic aqueous passivation composition is prepared which is applied to metallic substrates.
- the liquid passivation composition initially comprises water, acid and silane-modified silicate compounds. But it can also contain additives that z. B. improve the storage stability, the processing properties or the anti-corrosive effect of the applied coating.
- additives can be added both during alkaline hydrolysis and during or after acidification. Especially preferred is the addition of additives after acidification.
- Typical additives are catalysts, wetting agents, corrosion inhibitors, stabilizers and defoamers. Individual additives are explained in more detail below in their action in the composition according to the invention:
- metal-oxygen compounds of the metals strontium, molybdenum, vanadium, titanium, zirconium, manganese and / or tungsten in the aqueous acidic passivation composition are used as corrosion inhibitors.
- One or more of the compounds listed below are preferably used in the aqueous acidic composition: salts or oxides of the abovementioned metals, vanadates, molybdate, titanates, zirconates, manganates, salts and oxides of strontium and their polycondensates, in particular potassium orthovanadate, potassium metavanadate, sodium orthovanadate, sodium metavanadate , Sodium wolfram, sodium paratungstate, vanadyl sulfate and vanadium pentoxide, as well as sodium molybdate and potassium molybdate.
- compounds of the metals molybdenum, vanadium and / or tungsten are used which dissociate in the aqueous, acidic composition for passivation and thereby release molybdenum, vanadium and / or tungsten ions.
- Molybdenum, vanadium and tungsten ions are incorporated into the coating applied to the metallic substrate and cause the build-up of a very good corrosion protection of the coating.
- composition for the passivation of metallic substrate are used as surface-active substances, a phosphonic acid or a mixture of phosphonic acids.
- organic phosphonic acids for example (1-hydroxyethane-1,1-diyl) biphosphonic acid, 2-phosphonobutane 1, 2,4-tricarboxylic acid, aminotrimethylene phosphonic acid, ethylenediamine tetramethylenephosphonic acid, hexamethylenediamine tetramethylenephosphonic acid, hydroxyethylaminodimethylenephosphonic acid, 2-phosphonobutane-1 , 2,3-tricarboxylic acid, Bishexamethylentriaminpentamethylen- phosphonic acid or Diethylentriaminpentamethylenphosphonklare or mixtures thereof.
- organic phosphonic acids for example (1-hydroxyethane-1,1-diyl) biphosphonic acid, 2-phosphonobutane 1, 2,4-tricarboxylic acid, aminotrimethylene phosphonic acid, ethylenediamine tetramethylenephosphonic acid, hexamethylenediamine tetramethylenephosphonic acid,
- salts of phosphonic acid may prove advantageous in connection with the invention.
- Particularly suitable are the phosphonates listed below, each used individually or in admixture: tetrasodium (1-hydroxyethane-1, 1-diyl) biphosphonate, trisodium (1-hydroxyethane-1, 1-diyl) biphosphonate, pentasodium ethylene diamintetramethylenephosphonat or heptasodium -Diethylenetriamine pentamethylenephosphonate.
- These salts dissociate in the aqueous, acidic passivating composition, so that the phosphonates are available as surface-active substances.
- Phosphonic acids and their derivatives can also be advantageously used in conjunction with vanadium and tungsten compounds in acidic aqueous compositions.
- the use of phosphonic acid or phosphonates has proved to be a surface-active substance.
- phosphonates allows faster acidification or acidification with less acid.
- a combination of phosphonates and phosphoric acid proves to be suitable for the preparation of passivation compositions having good corrosion properties.
- the acidic aqueous passivating compositions for metallic substrates comprise one or more elements or compounds of the group comprising di-, trivalent or tetravalent metal ions.
- a passivation composition comprising silane-modified silicates of the composition described above and divalent, trivalent or tetravalent metal cations or a mixture of such metal cations is provided.
- aluminum and iron as trivalent cations and magnesium, zinc and manganese as divalent cations.
- the metal cations may also be incorporated into the passivation composition as salts of acids, preferably as salts of the acids used for acidification.
- phosphonates or bisphosphonates can be used which are obtained by dissolving the metals in phosphoric acid.
- Preferred anions when using salts of the abovementioned elements are, in addition to phosphates or phosphonates, acetates, chlorides, nitrates, sulfates and carbonates.
- the aqueous acidic passivating compositions according to the invention for metallic substrates in general are suitable for all metallic surfaces or substrates, but particularly well for workpieces with a surface of steel, iron, aluminum or zinc, but especially for workpieces whose surface with an alloy of one or both of the metals aluminum and zinc is provided with further metals.
- a zinc-aluminum alloy, an aluminum alloy or a zinc alloy with further metals, such as, for example, are typically suitable.
- iron or magnesium for.
- As with a zinc-iron alloy all of which can be provided with a corrosion protection coating.
- the layer thickness of the applied coating of metal or alloy is between 5 ⁇ and 100 ⁇ .
- the metallic alloy deposited on a substrate shows up as a discrete layer.
- metal ions can be incorporated into the passivation layer and z. B. be detected as Zn / Fe silicate.
- Typical applications for an aqueous acidic passivation composition comprising a silane-modified silicate compound are the passivation of electrolytic galvanized general cargo or bulk bulk material, in particular screws and stamped and bent parts and the coil coating, ie the passivation of steel strip.
- the passivation composition according to the invention can be applied as a single coating to a metallic substrate. However, this passivation composition may also be applied in conjunction with other coating compositions, for example, the acidic passivation according to this invention may be coated with an alkaline passivation.
- Table 1 shows in the left column next to water, first the silanes used in connection with the embodiments, in the lines below are listed particularly suitable silicates, which were used to carry out the alkaline condensation and hydrolysis. This is followed in the lines below various organic and inorganic acids, which are used to acidify the wholly or partially alkaline hydrolyzed silanes or siloxanes and silane-modified silicates. Finally, phosphonic acids are listed, which are used as surface-active systems. In two cases, sodium permanganate is used.
- silicate component ie individual silicates or mixtures of silicates
- the silane component ie individual silanes or mixtures of silanes, optionally with the addition of titanates or zirconates, was added dropwise with stirring.
- the dropwise addition of the silane component was carried out over a period of three hours; after complete dropwise addition of the silane component, stirring is continued for a further three hours.
- the silane component is largely hydrolyzed and condensed with the silicate, but it can not be ruled out that even in comparison to the alkaline hydrolysis but low hydrolysis in an acidic medium is possible. It has been found that to prepare a passivation composition having good anticorrosion properties it is not necessary for the hydrolysis to be complete in the alkaline. It is also possible to carry out the hydrolysis only partially in the alkaline, for example, to half or two-thirds and then to hydrolyze in an acidic medium to the end. To this alkaline hydrolyzate is then added the acid component, again with stirring over a period of three hours.
- the aim is to set a pH of equal to or less than 4 by addition of an acid or a mixture of acids. After reaching the desired pH of a maximum of 4 is stirred for a further three hours.
- the passivation composition and reference compositions obtained as a result of this preparation process are each knife-coated onto hot-dip galvanized steel sheets (DC 54 Z 100) and subjected to a salt spray test in accordance with DIN EN ISO 9227, the first forming white rust being evaluated.
- test results with a white rust resistance of 24 hours to 48 hours were rated as satisfactory results (0), test results with a white rust resistance of more than 48 Hours to 72 hours were rated as good (+) and test results with a white rust resistance greater than 72 hours were rated as excellent (++).
- the silane component was used in a weight ratio to the silicate component of 0.16: 1 to 2.1: 1. The best corrosion protection results were achieved when a weight ratio between silane component and silicate component of 0.4: 1 and 1: 1 was set.
- the corrosion inhibitors were added alone or in admixture to carry out the experiments presented in Table 1 already during the alkaline hydrolysis in an amount of 0.1% by weight to 5% by weight based on the total composition. However, they can also be added with equivalent effect only during or after the acidification.
- the surface-active substances are added during acidification based on the total composition in an amount of 0, 1 wt .-% to 2 wt%.
- the silane-modified silicates thus prepared were applied by doctoring to galvanized iron sheets.
- the dried layer which can be detected on the galvanized iron sheets, has a layer thickness of about 150 nm, unless otherwise stated.
- the silane and silicate components can not only be used in relation to each other within a wide range of proportions.
- the proportion of silane and silicate component used to make the silane-modified silicate passivation composition can be varied within very wide limits to accommodate a variety of application requirements. It is noteworthy that the experiments with a low proportion of silane and silicate components (Experiments 16-18) provide excellent corrosion protection results, even without the use of corrosion inhibitors. With the Passivi mecanicszu- compositions that were prepared according to experiments 16-18, particularly thin coatings of z. B. below 150 nm.
- the solids content of the passivation composition obtained by the process according to the invention is preferably between 3% and 66%, more preferably between 3.1% and 36%.
- lithium polysilicate generally produces good and outstanding corrosion protection results, unlike, for example, B. soda water glass alone.
- organic acids are just as well suited as inorganic acids.
- particularly good to excellent corrosion protection results are achieved when phosphoric and / or phosphonic acid is added.
- the phosphonic acids or phosphonates known as corrosion inhibitors are likewise suitable for acidifying the alkali-hydrolyzed silane-modified silicates and are already present in small amounts of 0.1% by weight and 1% by weight (see, for example, Experiment 3, 7, 15 and 20) are capable of producing satisfactory corrosion protection results. This is due to the fact that phosphonates often still have acidic residual functionalities that lead to the lowering of the pH after addition of the phosphonates.
- Table 1 a formulations for the preparation of silane-modified silicates obtained by alkaline hydrolysis at a pH between 9 and 1 1 and Table 1 a - continued
- the passivation composition according to the invention is prepared by firstly GLYMO 3-glycidyloxypropyltrimethoxysilane (Evonik) and DAMO n- (2-aminoethyl) -3-aminopropyltrimethoxysilane (Evonik); each 100% substance, in the ratio 1: 1 mixed 0 and 24 hours at 30 ° C under atmospheric humidity or optionally added water (1%) is stirred.
- the oligomer or polymer based on silanes thus obtained is added according to the invention in a ratio of 30:70 oligomer: silicate, based on the silicate solids.
- lithium polysilicate is used with 23% solids.
- a pH of 4 is set according to the invention by the addition of acid or salts.
- HEDP 1-Hydroxyethan- (1 -1 -diphosphonic acid
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Abstract
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Priority Applications (6)
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CN201580071635.3A CN107109658A (zh) | 2014-12-30 | 2015-12-22 | 包含硅烷改性的硅酸盐化合物的钝化组合物 |
US15/539,879 US10792702B2 (en) | 2014-12-30 | 2015-12-22 | Passivation composition comprising a silane-modified silicate compound |
JP2017532609A JP6936731B2 (ja) | 2014-12-30 | 2015-12-22 | シラン変性シリケート化合物を含む不動態化組成物 |
CN202211341641.4A CN115679310A (zh) | 2014-12-30 | 2015-12-22 | 包含硅烷改性的硅酸盐化合物的钝化组合物 |
KR1020177017106A KR20170102468A (ko) | 2014-12-30 | 2015-12-22 | 실란-변형된 실리케이트 화합물을 포함하는 패시베이션 조성물 |
US16/877,575 US11759820B2 (en) | 2014-12-30 | 2020-05-19 | Passivation composition comprising a silane-modified silicate compound |
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EP14200636.0A EP3040445B1 (de) | 2014-12-30 | 2014-12-30 | Passivierungszusammensetzung aufweisend eine silanmodifizierte Silikatverbindung |
EP14200636.0 | 2014-12-30 |
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US15/539,879 A-371-Of-International US10792702B2 (en) | 2014-12-30 | 2015-12-22 | Passivation composition comprising a silane-modified silicate compound |
US16/877,575 Continuation US11759820B2 (en) | 2014-12-30 | 2020-05-19 | Passivation composition comprising a silane-modified silicate compound |
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JP (1) | JP6936731B2 (de) |
KR (1) | KR20170102468A (de) |
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EP3428314A1 (de) | 2017-07-14 | 2019-01-16 | Ewald Dörken Ag | Zusammensetzung und verfahren zur passivierung verzinkter bauteile |
EP4332176A1 (de) | 2022-09-02 | 2024-03-06 | Ewald Dörken Ag | Wässrige beschichtungszusammensetzung und ihre verwendung |
EP4332177A1 (de) | 2022-09-02 | 2024-03-06 | Ewald Dörken Ag | Wässrige beschichtungszusammensetzung und ihre verwendung |
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TWI600725B (zh) * | 2016-09-29 | 2017-10-01 | 3M創新有限公司 | 一種具有防滑功能的保護性塗層組合物、塗佈製品及其製備方法 |
FR3074185B1 (fr) * | 2017-11-28 | 2021-04-09 | Nof Metal Coatings Europe | Compositions de revetement deshydratees, sous forme solide, leur procede d'obtention et leur procede de rehydratation |
KR102031251B1 (ko) * | 2019-03-06 | 2019-10-11 | 영창케미칼 주식회사 | 실리콘질화막 식각 조성물 |
US20210198522A1 (en) * | 2019-12-31 | 2021-07-01 | Industrial Technology Research Institute | Water-based coating material and method for manufacturing the same |
CN111254426A (zh) * | 2020-02-04 | 2020-06-09 | 桂林理工大学 | 一种Zn-SiC复合镀层的硅酸盐彩色钝化方法 |
FR3130854A1 (fr) | 2021-12-21 | 2023-06-23 | Nof Metal Coatings Europe | Revêtement anticorrosion |
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CN115679310A (zh) | 2023-02-03 |
ES2721434T3 (es) | 2019-07-31 |
US10792702B2 (en) | 2020-10-06 |
EP3040445A1 (de) | 2016-07-06 |
US11759820B2 (en) | 2023-09-19 |
EP3040445B1 (de) | 2019-02-06 |
JP2018500464A (ja) | 2018-01-11 |
JP6936731B2 (ja) | 2021-09-22 |
US20200276610A1 (en) | 2020-09-03 |
US20170348730A1 (en) | 2017-12-07 |
CN107109658A (zh) | 2017-08-29 |
KR20170102468A (ko) | 2017-09-11 |
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