WO2009095375A1 - Verfahren zur beschichtung von metallischen oberflächen mit einer schmierstoffzusammensetzung - Google Patents
Verfahren zur beschichtung von metallischen oberflächen mit einer schmierstoffzusammensetzung Download PDFInfo
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- WO2009095375A1 WO2009095375A1 PCT/EP2009/050854 EP2009050854W WO2009095375A1 WO 2009095375 A1 WO2009095375 A1 WO 2009095375A1 EP 2009050854 W EP2009050854 W EP 2009050854W WO 2009095375 A1 WO2009095375 A1 WO 2009095375A1
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- Prior art keywords
- lubricant composition
- coating
- water
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- ionomer
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M173/00—Lubricating compositions containing more than 10% water
- C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21J—FORGING; HAMMERING; PRESSING METAL; RIVETING; FORGE FURNACES
- B21J3/00—Lubricating during forging or pressing
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
- C10M111/04—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a macromolecular organic compound
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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
- C23C22/60—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 alkaline aqueous solutions with pH greater than 8
- C23C22/62—Treatment of iron 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
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/04—Elements
- C10M2201/041—Carbon; Graphite; Carbon black
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/06—Metal compounds
- C10M2201/062—Oxides; Hydroxides; Carbonates or bicarbonates
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/06—Metal compounds
- C10M2201/065—Sulfides; Selenides; Tellurides
- C10M2201/066—Molybdenum sulfide
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- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/10—Compounds containing silicon
- C10M2201/102—Silicates
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/022—Ethene
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- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/024—Propene
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/16—Paraffin waxes; Petrolatum, e.g. slack wax
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/18—Natural waxes, e.g. ceresin, ozocerite, bees wax, carnauba; Degras
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/084—Acrylate; Methacrylate
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/084—Acrylate; Methacrylate
- C10M2209/0845—Acrylate; Methacrylate used as base material
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/044—Polyamides
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/045—Polyureas; Polyurethanes
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- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/046—Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/02—Esters of silicic acids
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/04—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions having a silicon-to-carbon bond, e.g. organo-silanes
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
- C10M2229/02—Unspecified siloxanes; Silicones
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/04—Molecular weight; Molecular weight distribution
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/24—Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/243—Cold working
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- C10N2040/20—Metal working
- C10N2040/244—Metal working of specific metals
- C10N2040/245—Soft metals, e.g. aluminum
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- C10N2040/244—Metal working of specific metals
- C10N2040/246—Iron or steel
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- C10N2040/244—Metal working of specific metals
- C10N2040/247—Stainless steel
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- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/015—Dispersions of solid lubricants
- C10N2050/02—Dispersions of solid lubricants dissolved or suspended in a carrier which subsequently evaporates to leave a lubricant coating
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- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/023—Multi-layer lubricant coatings
- C10N2050/025—Multi-layer lubricant coatings in the form of films or sheets
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2080/00—Special pretreatment of the material to be lubricated, e.g. phosphatising or chromatising of a metal
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- 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 process for coating metallic surfaces with a lubricant composition in the form of an aqueous solution or dispersion based on polymeric organic material containing at least one water-soluble, hydrous o- / / and water-binding oxide and / or silicate and at least one organic polymeric material comprising ionomer, further polymer / copolymer or derivatives thereof and, if appropriate, at least one solid lubricant, at least one friction modifier and / or at least one further additive and a corresponding lubricant composition which, after the formation of a coating on a metallic lubricant Shaped body in particular to facilitate the cold forming of this shaped body to serve.
- Cold forming can usually take place at surface temperatures of up to about 450 ° C. but without the supply of heat. The heating occurs only by the deformation and optionally the preheating of the workpieces to be formed. Typically, the temperature of the to be shaped workpieces, however, but is at about 20 0 C. If the re-shaped workpieces at temperatures in the range 650-850 0 C or 900-1250 0 C in advance are heated, it is called warm or hot forming.
- Cold forming includes: A sliding pull (train pressure conversion) eg of welded or seamless pipes, hollow profiles, bars, solid profiles or wires, ironing and / or deep drawing eg of strips, sheets or hollow bodies into hollow bodies
- Cold extrusion e.g. of hollow or solid bodies or / and cold heading, e.g. from wire sections to connectors such as e.g. Nut or screw blanks.
- the cold-forming metal moldings have been made almost exclusively by either applying a grease, an oil, or an oil emulsion, or first by coating with zinc phosphate and then by coating either with a soap based on alkali or alkaline earth metal stearate or / and prepared with a solid lubricant in particular based on molybdenum sulfide, tungsten sulfide or / and carbon.
- a soap-containing coating will find its upper limit of use at medium and mid-high temperatures.
- a solid lubricant was only used if it was medium or heavy cold forming. In the cold forming of stainless steels often laminations of chlorinated paraffins were used, which are today reluctantly used for reasons of environmental protection. But sulfide-containing coatings affect stainless steel.
- DE-A-44 45 993 describes a lubricant concentrate for cold forming with a content of polyethylene, polyacrylic acid and styrene / acrylic acid copolymer of certain properties and the corresponding method for applying the lubricant coating.
- Waxes are not explicitly mentioned.
- this lubricant system has the disadvantage that the viscosity drops relatively sharply at high temperature, and that even in the case of medium-heavy forming, a solid lubricant, such as, for example, is obtained.
- Molybdenum disulfide and / or graphite required.
- the sulfidic solid lubricants are necessary especially at high temperature. But they have the disadvantage that the sulfides are not resistant to hydrolysis and are easily converted into sulfurous acid. The sulfurous acid can easily cause corrosion if the coating is not removed from the workpiece immediately after cold working.
- the abovementioned lubricant systems do not fulfill the meanwhile much more stringent demands on the forming size, the ejection accuracy (net-shape) and the forming speed.
- environmental compatibility and workplace hygiene must be taken into account.
- the excess lubricant residues should not be deposited at one point on the tool. Because this influences the extrusion accuracy of the workpieces and increases rejects. It is advantageous if the coating and deposits can be easily removed from the workpiece, tool and equipment after forming.
- the coating should be able to be removed in a simple manner if necessary after the cold forming of the formed workpiece.
- a lubricant layer coating
- this product spectrum would today be treated first with a zinc phosphate layer, then with a conventional organic-polymeric lubricant composition and optionally additionally, if necessary, additionally coated with a third coating based on sulfidic solid lubricant and optionally additionally of graphite.
- Sulphide solid lubricant was necessary for all medium and heavy cold forming operations.
- the organic-polymeric lubricant composition which is significantly higher in quality than the soap coating, has been isolated despite the higher cost. However, it was free of water-soluble, water-containing or / and water-binding oxides or / and silicates. In this sequence, about 40% of the product spectrum would require the additional third coating. If a zinc phosphate layer is used as the first coating and the lubricant composition according to the invention as the second coating, an additional third coating based on sulfidic solid lubricant is now required only at 12 to 20% of the product spectrum.
- the inventive method is used in particular to facilitate, improve or / and simplify the cold forming of metallic moldings.
- lubricant composition denotes the stages from the aqueous over the drying to the dry lubricant composition as the chemical composition, phases related composition and composition relating to mass, while the term “coating” refers to the dry, heated, softening and / or melting coating is formed from the lubricant composition and / or formed, including its chemical composition, phase-related composition and composition referred to composition.
- the aqueous lubricant composition may be a dispersion or solution, especially a solution, colloidal solution, emulsion and / or suspension. It usually has a pH in the range from 7 to 14, in particular from 7.5 to 12.5 or from 8 to 11, 5, particularly preferably from 8.5 to 10.5 or from 9 to 10.
- the lubricant composition or / and the coating formed therefrom contains / contains at least one water-soluble or at least one ionomer, at least one non-ionomer and / or at least one wax and optionally a content of at least one additive.
- it additionally particularly preferably contains in each case at least one content of acrylic acid / methacrylic acid or / and styrene, in particular as polymer (s) or copolymer (s), which is / are no ionomer (s).
- the lubricant composition and / or the coating formed therefrom each contain / contain at least 5% by weight of at least one ionomer and / or non-ionomer.
- the organic polymeric material preferably consists essentially of monomers, oligomers, cooligomers, polymers or / and copolymers based on ionomer, acrylic acid / methacrylic acid, epoxide, ethylene, polyamine, propylene, styrene, urethane, their ester (s) or / and their salt (s).
- ionomer here includes a content of free and / or associated ions.
- the water-soluble, water-containing or / and water-binding oxide or / and silicate may preferably each comprise at least one water glass, a silica gel, a silica sol, a silica hydrosol, a silicic acid ester, an ethyl silicate and / or at least one of their precipitated products, hydrolysis products, condensation products or / and reaction products, in particular a lithium, sodium or / and potassium-containing water glass.
- a content of water in the range of 5 to 85 wt .-% based on the content of solids bound or / and coupled to the water-soluble, hydrous and / or water-binding oxide o- / silicate and / or coupled, preferably in the range of 10 to 75, from 15 to 70, from 20 to 65, from 30 to 60 or from 40 to 50 wt .-%, wherein the typical water content may have significantly different water contents depending on the nature of the oxide or / and silicate.
- the water may, for example, due to the solubility, adsorption, Wetting, chemical bonding, porosity, complex particle shape, complex aggregate form or / and intermediate layers bound to the solid and / or be coupled.
- water-bound or / and coupled substances apparently act in the lubricant composition and / or in the coating similar to a sliding layer. It is also possible to use a mixture of two or at least three substances of this group.
- other cations may be present, in particular ammonium ions, alkali ions other than sodium and / or potassium ions, alkaline earth metal ions and / or transition metal ions. The ions may be or have been at least partially replaced.
- the water of the water-soluble, aqueous o- / / and water-binding oxide and / or silicate can be at least partially adsorbed as water of crystallization, as a solvent, bound to pore space, in a dispersion, in an emulsion, in a gel and / or in a sol available.
- Particularly preferred is at least one water glass, in particular a sodium-containing water glass.
- it may also contain a content of at least one oxide such as, in each case, at least one silicon dioxide or / and magnesium oxide and / or at least one silicate, for example at least one layered silicate, modified silicate and / or alkaline earth silicate.
- this is in each case at least one oxide or / and silicate in dissolved form, in nanocrystalline form, as gel and / or as sol.
- a solution may also be present as a colloidal solution.
- the water-soluble, water-containing or / and water-binding oxide or / and silicate is present in particulate form, it is preferably very fine-grained, in particular with an average particle size of less than 0.5 ⁇ m, less than 0.1 or even less than 0.03 ⁇ m, respectively determined with a laser particle measuring device and / or nanoparticle measuring device.
- the water-soluble, hydrous and / or water-binding oxides or silicates help to increase the viscosity of the dried, emollient and melting coating and have many effects as binders, as water repellents and as corrosion inhibitors. It has been found that among the water-soluble, water-containing or / and water-binding oxides and / or silicates, water glass behaves particularly favorably.
- the viscosity of the dried, softening and melting coating in many embodiments, especially at temperatures of more than 230 0 C significantly increased in Comparison to a lubricant composition on the same chemical basis, but without the addition of waterglass.
- a higher mechanical stress during cold forming is possible. This made it possible for many compositions and applications only to apply a cold extrusion, which was not applicable without this addition.
- the tool wear and the number of tool changes can be drastically reduced. The production costs are thereby also significantly reduced.
- a disilicate additive has also proved to be advantageous.
- the content of water-soluble, hydrous or / and water-binding oxides or / and silicates in the lubricant composition and / or in the coating formed therefrom is preferably 0.1 to 85, 0.3 to 80 or 0.5 to 75 wt .-% of the solid - And active ingredients, more preferably 1 to 72, 5 to 70, 10 to 68, 15 to 65, 20 to 62, 25 to 60, 30 to 58, 35 to 55 or 40 to 52 wt .-% of the solids and active ingredients , determined without the bound or / and coupled water content.
- the weight ratio of the contents of water-soluble, hydrous or / and water-binding oxides or / and silicates to the content of ionomer (s) and / or non-ionomer (s) in the lubricant composition or / and in the coating is preferably in the range from 0.001: 1 to 0.2: 1, more preferably in the range of 0.003: 1 to 0.15: 1, from 0.006: 1 to 0.1: 1 or from 0.01: 1 to 0.02: 1.
- the ionomers are a special type of polyelectrolytes. They preferably consist essentially of ionomeric copolymers, optionally together with corresponding ions, monomers, comonomers, oligomers, cooligomers, polymers, their esters or / and their salts. Block copolymers and graft copolymers are considered to be a subgroup of the copolymers.
- the ionomers are compounds based on acrylic acid / methacrylic acid, ethylene, propylene, styrene, their esters or their salt (s) or mixtures with at least one of these ionomeric compounds.
- the lubricant composition and / or the coating formed therefrom may either contain no content or content of at least one ionomer in the range of from 3 to 98% by weight of the solids and active ingredients.
- the content of at least one ionomer is from 5 to 95, 10 to 90, 15 to 85, 20 to 80, 25 to 75, 30 to 70, 35 to 65, 40 to 60 or 45 to 55 wt .-% of the solid and active ingredients of the lubricant composition and / or the coating formed therefrom.
- the composition of the lubricant composition and / or the coating formed therefrom may vary and vary widely.
- the lubricant composition and / or the coating formed therefrom may preferably contain at least one ionomer having a substantial content of at least one copolymer, in particular a copolymer based on polyacrylic, polymethacrylic, polyethylene or / and polypropylene.
- an ionomer has a glass transition temperature T 9 in the range of - 30 0 C to + 40 0 C, preferably in the range of - 20 to + 20 0 C.
- the molecular weight of the ionomer is preferably in the range of 2,000 to 15,000, more preferably in Range from 3,000 to 12,000 or from 4,000 to 10,000.
- the lubricant composition or / and the coating formed therefrom particularly preferably contains / contains at least one ionomer based on ethylene acrylate and / or ethylene methacrylate, preferably one having a molecular weight in the range from 3,500 to 10,500, more preferably in the range from 5,000 to 9,500 / and with a glass transition temperature T 9 in the range of - 20 0 C to + 30 0 C.
- the acrylate content may be up to about 25 wt .-%.
- a slightly higher molecular weight may be advantageous for higher loadable coatings.
- Some ionomer additives also serve to ensure lubrication and reduce friction in the early stages of cold forming, especially when the workpiece is cold and the tool is cold. This is all the more important the easier and / or weaker the cold forming is and the lower the forming temperature is.
- the melting point of at least one ionomer is in many embodiments preferably in the range of 30 to 85 0 C. Its glass transition temperature is preferably below 35 0 C. At least one ionomer is preferably added as a dispersion.
- organic polymeric constituents may be present, e.g. Oligomers, polymers or / and copolymers based on acrylic acid / methacryic acid, amide, amine, aramid, epoxide, ethylene, imide, polyester, propylene, styrene, urethane, their ester (s) or / and their salts
- some acrylic-containing polymers / copolymers and some styrene acrylates may act as thickeners.
- Polyethylene or polypropylene may preferably be modified by propylene, ethylene, their corresponding polymers or / and by further additives such as acrylate. They may preferably have waxy properties. They may preferably have at least one softening range / softening point and / or at least one melting range / melting point in the range from 80 to 250 ° C.
- the polymers or / and copolymers of these substances preferably have a molecular weight in the range of 1,000 to 500,000.
- Individual substances preferably have a molecular weight in the range of 1,000 to 30,000, others one in the range of 25,000 to 180,000 or / and in the range of 150,000 to 350,000.
- Particularly high molecular weight substances can be used as thickeners.
- An acrylic and / or styrene acrylate additive can also have a thickening effect.
- one or two, three, four or five different non-ionomers are added to the ionomer-containing lubricant composition and / or coating.
- the lubricant composition and / or the coating formed therefrom preferably does not have a content or content of at least one non-ionomer in the range of 0.1 to 90% by weight of the solids and the active ingredients.
- the content of the at least one non-ionomer is particularly preferably 0.5 to 80, 1 to 65, 3 to 50, 5 to 40, 8 to 30, 12 to 25 or 15 to 20 wt .-% of the solids and active ingredients the lubricant composition or the coating.
- Both the individual or the premixed ionomers, as well as the individual or premixed non-ionomers can each, independently from each other, as a solution, colloidal solution, dispersion and / or emulsion of the aqueous lubricant composition may be added.
- the lubricant composition contains non-ionomers which are not waxes in the context of this application:
- the ionomers and / or non-ionomers may be present, at least partially, in particular the acrylic acid components of the polymers according to b) and c), preferably partially under application conditions, in particular predominantly or completely, as salts of inorganic or / and organic cations.
- the weight ratio of the contents of ionomer (s) to non-ionomer (s) is preferably in the range of 1: 3 to 50: 1, more preferably in the range of 1: 1 to 35 : 1, from 2: 1 to 25: 1, from 4: 1 to 18: 1 or from 8: 1 to 12: 1.
- the lubricant composition and / or the coating produced therewith have a total content of at least one ionomer in each case and / or non-ionomer preferably from zero or in the range of from 3 to 99% by weight of the solids and active ingredients.
- This content is particularly preferably 10 to 97, 20 to 94, 25 to 90, 30 to 85, 35 to 80, 40 to 75, 45 to 70, 50 to 65 or 55 to 60 wt .-% of the solids and active ingredients of Lubricant composition and / or coating.
- Thickeners based on non-ionomers are included here.
- the content of ionomer (s) or / and non-ionomer (s) can vary within wide limits. At least one content of at least one ionomer is particularly preferred.
- the entire organic polymeric material - this term is intended to include ionomer (s) or / and non-ionomer (s) but not waxes - has an average acid number in the range of from 20 to 300, more preferably in the range of from 30 to 250 40 to 200, from 50 to 160 or from 60 to 100.
- the term "all organic polymeric material” is intended to include ionomer (s) and / or non-ionomer (s) but not waxes.
- At least one alkylamine of at least one aminal alcohol or / and of at least one amine related thereto, for example in each case at least one alkanolamine, an aminoethanol, an aminopropanol, a diglycolamine, an ethanolamine, an ethylenediamine Monoethanolamine, a diethanolamine or / and a triethanolamine, in particular dimethylethanolamine, 1- (dimethylamino) -2-propanol or / and 2-amino-2-methyl-1-propanol (AMP).
- alkanolamine an aminoethanol, an aminopropanol, a diglycolamine
- an ethanolamine an ethylenediamine Monoethanolamine
- a diethanolamine or / and a triethanolamine in particular dimethylethanolamine, 1- (dimethylamino) -2-propanol or / and 2-amino-2-methyl-1-propanol (AMP).
- AMP 2-amino-2-methyl-1-propanol
- the at least one organic salt in particular at least one salt of inorganic or / and organic cations such as ammonium ions, can be obtained, for example, by adding at least one neutralizing agent to at least one ionomer and / or at least one non-ionomer or / and to a mixture containing at least one these polymeric organic materials and optionally at least one further component such as at least one wax and / or at least one additive contains, are formed.
- the salt formation can take place before or / and in the preparation of the lubricant composition or / and in the lubricant composition.
- the neutralizing agent in particular at least one amine alcohol, forms many times in the temperature range from room temperature to about 100 0 C, in particular at temperatures in the range of 40 to 95 0 C, with at least one ionomer and / or with at least one non-ionomer corresponding salts. It is believed that in some embodiments, in particular at least one amine alcohol, the neutralizing agent may chemically react with the water-soluble, hydrous and / or water-binding oxide and / or silicate and thereby form a reaction product that beneficially behaves for cold working.
- Aqueous lubricant compositions with an addition of ammonia should preferably not be heated above 30 0 C.
- Aqueous lubricant compositions with an addition of at least one amine should preferably be kept in a temperature range of 60 to 95 0 C, in which many reactions take place to amine salts.
- At least one neutralizing agent such as at least one amine or / and at least one amine alcohol
- the reactions to corresponding salts preferably proceed with water-soluble or / and water-dispersed organic polymeric materials.
- the at least one neutralizing agent in particular at least one amine, is added at an early stage in the mixing together of the various components of the aqueous lubricant composition and thereby possibly minimized.
- at least one already contained organic polymeric material and / or at least one thereafter added organic polymeric material is at least partially neutralized.
- the neutralizing agent is added in excess or / and is contained in the lubricant composition and / or in the coating in excess.
- the at least one neutralizing agent in particular the at least one amine alcohol, can also be used to adjust the pH of a mixture or of the aqueous lubricant composition.
- the organic salts have the advantage over ionomers and / or non-ionomers of being often more water-soluble or better water-dispersible than the corresponding ionomers and / or non-ionomers.
- the coatings and deposits from cold forming can be better removed from the formed workpiece.
- lower softening ranges / softening points or / and lower melting ranges / melting points result with the organic salts, which is often advantageous.
- also better lubricating shafts are obtained for the desired processing conditions.
- organic salts especially amine salts and / or organic ammonium salts are preferred.
- amine salts since, after application of the aqueous lubricant composition, they do not change their composition more strongly and have higher water solubility and / or water dispersibility and therefore contribute comparatively easily to the coating and the deposits on the formed workpiece after cold forming remove.
- the organic ammonium salts after application of the aqueous lubricant composition, ammonia quickly escapes, which is not the only thing may represent an odor nuisance, but also causes a back reaction of the ammonium salts to the original organic polymeric substances, which then later can be removed worse than the amine salts. This results in chemically and in water quite stable coatings.
- hydroxide (s) as a neutralizing agent often results in fairly hard and brittle, but water-sensitive coatings.
- the content of the at least one neutralizing agent, in particular also the at least one Aminalkohols, in the lubricant composition may - especially depending on the acid number of the ionomer or non-ionomer - at the beginning of the neutralization reaction preferably at zero or in the range of 0.05 to 15, from 0 , 2 to 12, from 0.5 to 10, from 0.8 to 8, from 1 to 6, from 1, 5 to 4 or from 2 to 3 wt .-% of the solids and active ingredients.
- Higher contents may be advantageous in some embodiments, in particular with the addition of at least one amine, while in the case of an addition of ammonia or / and at least one hydroxide, rather lower contents are selected in most embodiments.
- the weight ratio of the neutralizing agent (s), in particular also of amino alcohol (s), to contents of ionomer (s) or / and non-ionomer (s) or / and to the total content of organic polymeric material is preferably in the range from 0.001: 1 to 0.2: 1, more preferably in the range from 0.003: 1 to 0.15: 1, from 0.006: 1 to 0.1: 1 or from 0.01: 1 to 0.05 : 1.
- the lubricant composition according to the invention or / and the coating formed therefrom preferably does not have a content or a content of at least one organic salt, which was preferably formed by neutralization, in the range from 0.1 to 95 or 1 to 90% by weight.
- the solids and active ingredients Preferably, the content of at least one salt is 3 to 85, 8 to 80, 12 to 75, 20 to 70, 25 to 65, 30 to 60, 35 to 55 or 40 to 50% by weight of the solid and active ingredients of the lubricant composition.
- the weight ratio of the contents of at least one organic salt at levels of ionomer (s) and / or non-ionomer (s) is in the lubricant composition or / and in the coating preferably in the range of 0.01: 1 to 100: 1, particularly preferably in the range of 0.1: 1 to 95: 1, from 1: 1 to 90: 1, from 2: 1 to 80: 1, from 3: 1 to 60: 1, from 5: 1 to 40: 1 or from 8: 1 to 20: 1 ,
- a wax is intended to mean a compound which has a defined melting point, which in the molten state has a fairly low viscosity and which is capable of occurring in crystalline form.
- a wax has no or no substantial content of carboxyl groups, is hydrophobic, and is highly chemically inert.
- the lubricant composition and / or the coating formed therefrom may preferably contain at least one wax, in particular at least one paraffin wax, a carnauba wax, a silicone wax, an amide wax, an ethylene and / or a propylene-based wax and / or a crystalline wax.
- it can serve to increase the lubricity and / or creep of the forming and / or formed coating, the separation of the workpiece and the tool and to reduce friction.
- the content of the individual wax is in each case in the range from 0.05 to 36% by weight of the solids and active substances in the lubricant composition or / and in the coating, particularly preferably in the range from 0.5 to 30, 1 to 25 , 2 to 20, 3 to 16, 4 to 12, 5 to 10 or 6 to 8 wt .-% of the solids and active ingredients.
- At least one wax may preferably have an average particle size in the range from 0.01 to 15 ⁇ m, particularly preferably in the range from 0.03 to 8 ⁇ m or 0.1 to 4 ⁇ m. With these particle sizes, it may be preferred in many embodiments if the wax particles at least partially protrude from the coating formed.
- the addition of at least one wax can be dispensed with, in particular if the cold forming is not too heavy and / or if a higher content of ionomer, waxy substance or / and water-soluble, hydrous and / or water-binding oxide and / or silicate is contained , Only with heavy cold extrusion with lubricant compositions of very high ionomer content can be dispensed with a wax additive. In most embodiments, however, an addition of at least one wax is advantageous.
- the at least partially softened or at least partially melting coating can raise during cold working on the workpiece to be formed and form a release film between the workpiece and the tool. As a result, e.g. Grooves in the workpiece are avoided.
- the weight ratio of the contents of at least one wax to the total content of ionomer (s) and / or non-ionomer (s) in the lubricant composition and / or in the coating formed therefrom is preferably in the range of 0.01: 1 to 8: 1 , more preferably in the range of 0.08: 1 to 5: 1, from 0.2: 1 to 3: 1, from 0.3: 1 to 2: 1, from 0.4: 1 to 1, 5: 1 , from 0.5: 1 to 1: 1 or from 0.6: 1 to 0.8: 1.
- different content ranges can be particularly advantageous: once very low, sometimes very high levels.
- a comparatively very high wax content is recommended for sliding pull, deep drawing and light to medium hard cold forming.
- a comparatively low wax content has been found to be sufficient for heavy cold extrusion or difficult sliding operations such as solid parts and extra thick wire.
- Particularly preferred is a content of two, three, four or more than four different waxes, in particular those having significantly different melting ranges / melting points and / or viscosities.
- the lubricant composition and / or the coating formed therefrom have a plurality of successive softening areas / softening points or / and melting areas / melting points over a larger temperature range, which is passed through the cold forming during heating of the metallic workpiece, in particular such that there is a substantially continuous change in the thermal and / or mechanical properties and / or viscosity of the lubricant composition and / or the softening / / melting and / or melting coating.
- the waxes in the lubricant composition and / or in the coating formed therefrom at least a melting range / melting point in the range of 50 to 120 0 C (for example, paraffin waxes), of 80 to 90 0 C (for example, carnauba wax), of 75 to 200 0 C (eg amide waxes), from 90 to 145 0 C (eg polyethylene waxes) or from 130 to 165 0 C (eg polypropylene waxes) on.
- Low-melting waxes can also serve to ensure lubrication and reduce friction in the early stages of cold forming, especially when the workpiece is cold and when the tool is cold.
- At least two low-melting waxes - for example, with at least one melting range / melting point T m in the range of 60 to 90 or 65 to 100 0 C - and / or at least two high-melting waxes - for example, with at least a melting range / melting point T m in the range of 110 to 150 or 130 to 160 0 C - to use.
- This is particularly advantageous if these waxes have significantly different viscosities at those low or high temperatures in the range of the melting range / melting point, whereby a certain viscosity can be set in the heated or / and melting lubricant composition.
- a high-melting amide wax be less viscous than a high-melting polyethylene or / and polypropylene wax.
- the waxes are spread over the desired processing range, in particular over the desired temperature range selected.
- the lubricant composition and / or the coating formed therefrom may contain at least one solid lubricant and / or at least one friction modifier.
- at least one such additive in the lubricant composition, in the coating formed therefrom and / or in the film formed on a coating on the basis of at least one solid lubricant is advantageous if high degrees of deformation are required.
- the total content of at least one solid lubricant and / or at least one friction modifier in the lubricant composition and / or in the coating formed therefrom is preferably either zero or in the range of 0.5 to 50, 1 to 45, 3 to 40, 5 to 35, 8 to 30, 12 to 25 or 15 to 20 wt .-% of the solids and active ingredients.
- At least one solid lubricant may be added to the lubricant composition and / or on the other hand a film containing at least one solid lubricant may be applied to the coating prepared with an aqueous lubricant composition.
- a film containing at least one solid lubricant may be applied to the coating prepared with an aqueous lubricant composition.
- the solid lubricant may preferably be molybdenum disulfide, tungsten sulfide, bismuth sulfide or / and amorphous or / and crystalline carbon. For reasons of environmental protection, heavy metal-free work is preferably also carried out. All of these solid lubricants have the disadvantage of strongly staining and heavily soiling.
- the sulfidic solid lubricants have the disadvantage that the sulfides are not resistant to hydrolysis and are easily converted into sulfurous acid. The sulfurous acid can easily cause corrosion if the solid lubricant containing coating and the solid lubricant containing deposits are not removed from the workpiece immediately after cold working.
- the sulfidic solid lubricants are particularly necessary for heavy cold forming and resulting medium to high temperature.
- the carbon additives are particularly advantageous at very high temperature and with a higher degree of deformation. While molybdenum disulfide can be used up to temperatures of about 450 0 C, graphite can be used up to temperatures of about 1100 0 C, but its
- Lubricating effect at the cold forming approximately at 600 0 C begins. Therefore, a mixture of molybdenum disulfide powder, preferably particularly finely ground, is often used together with graphite or / and amorphous carbon. But carbon addition can lead to undesirable carburizing of an iron material. And sulfide addition can even lead to intercrystalline corrosion in stainless steel.
- the lubricant composition of the present invention and / or the coating formed therefrom preferably has no content or content of at least one solid lubricant in the range of 0.5 to 50, 1 to 45, 3 to 40, 5 to 35, 8 to 30, 12 to 25 or 15 to 20 wt .-% of the solids and active ingredients.
- At least one of the following substances may be used in the lubricant composition: alkali nitrate, alkali formate, alkali propionate, phosphoric acid ester - preferably as an amine salt, thiophosphate, e.g. Zinc dialkyl dithiophosphate, thiosulfate and / or alkali metal pyrophosphate - the latter preferably combined with alkali metal thiosulfate.
- They participate in many embodiments in the formation of a protective layer and / or a release layer for separating workpiece and tool and help to avoid cold welding between the workpiece and tool. But they can be partially corrosive. Because the phosphorus and / or sulfur-containing additives can react chemically with the metallic surface.
- the lubricant composition of the invention and / or the coating formed therefrom preferably has / does not have a content or a content of at least one coefficient of friction in the range from 0.05 to 5 or 0.1 to 4% by weight of the solids and active substances, especially preferably in the range of 0.3 to 3, from 0.5 to 2.5 or from 1 to 2 wt .-%.
- the lubricant composition and / or the coating formed therefrom may each contain at least one additive. It may contain at least one additive selected from the group consisting of wear-protective additives, silane additives, elastomers, film-forming auxiliaries, corrosion inhibitors, surfactants, defoamers, leveling agents, biocides, thickeners and organic solvents.
- the total content of additives in the lubricant composition and / or in the coating formed therefrom is preferably in the range of 0.005 to 20, 0.1 to 18, 0.5 to 16, 1 to 14, 1 to 5 to 12, 2 to 10, 2 , 5 to 8, 3 to 7 or 4 to 5.5 wt .-% of the solids and active ingredients.
- Thickeners based on non-ionomers are excluded at these levels and are taken into account in non-ionomers.
- the content and the choice of additives can vary within wide limits.
- At least one of the following substances may be used to act as wear-protecting additives and / or as friction modifiers:
- the lubricant composition according to the invention and / or the coating formed therefrom preferably does not have a content or a content of at least one wear-protecting organic substance in the range from 0.1 to 10 or 0.5 to 8% by weight of the solids and active substances on. Preferably, this content is 1 to 6, 2 to 5 or 3 to 4 wt .-% of the solids and active ingredients.
- aqueous solutions containing at least one silane additive in concentrations in the range from 5 to 50% by weight, in particular also an 8%, a 12% and an 18% solution, based on at least one silane have been used in experiments.
- Silanol / siloxane based on ⁇ -aminopropyltriethoxysilane, diaminosilane or / and 1, 2-bis (thmethoxysilyl) ethane used to pre-rinse the phosphated workpiece, dried and then coated with the lubricant composition.
- this solution may also be mixed with the aqueous lubricant composition. In both variants, this addition had a significant improvement in lubricity.
- a silane with at least one Amino group such as an aminoalkylsilane
- a silane having at least one succinic group and / or succinic anhydride group a bis-silyl silane
- It may preferably contain at least one elastomer, in particular a hydroxy-terminated polysiloxane, preferably having a molecular weight greater than 90,000, for increasing lubricity and scratch resistance, in particular at a content of from 0.01 to 5 or from 0.2 to 2.5 % By weight of the solid and active substances of the lubricant composition or / and of the coating.
- at least one elastomer in particular a hydroxy-terminated polysiloxane, preferably having a molecular weight greater than 90,000, for increasing lubricity and scratch resistance, in particular at a content of from 0.01 to 5 or from 0.2 to 2.5 % By weight of the solid and active substances of the lubricant composition or / and of the coating.
- It may preferably contain at least one film-forming auxiliary for the production of a substantially or completely closed organic coating.
- the cold-working coating will not be fully closed, which is quite sufficient for these applications when subsequently removed from the formed workpiece.
- the addition of at least one film-forming aid may be advantageous.
- a film formation under the action of the at least one film-forming auxiliary can be carried out in particular together with corresponding non-ionomers and, for example, with water glass.
- the film can be formed, in particular, together with ionomers, non-ionomers and, for example, with water glass.
- film-forming aids are usually se long-chain alcohols or / and alkoxylates used.
- film-forming auxiliaries are usually se long-chain alcohols or / and alkoxylates used.
- the level of film-forming assistant (s) in the lubricant composition is in the range of 0.03 to 5% by weight of the lubricants and / or coating solids and / or the coating, more preferably 0.1 to 2% by weight.
- the weight ratio of organic film-forming agent contents to film-forming aids in the lubricant composition is preferably in the range of 10: 1 to 400: 1, 20: 1 to 250: 1, or 40: 1 to 160: 1, more preferably in the range of 50: 1 to 130: 1, from 60: 1 to 110: 1 or from 70: 1 to 100: 1.
- the lubricant composition of the invention may preferably contain at least one anticorrosive agent, e.g. based on carboxylate, dicarboxylic acid, organic amine salt, succinate or / and sulfonate.
- at least one anticorrosive agent e.g. based on carboxylate, dicarboxylic acid, organic amine salt, succinate or / and sulfonate.
- Such an additive may be applied in particular to coatings which are to remain on the reshaped workpiece at least partially permanently, and / or at the risk of rusting, e.g. in Flash Rusting, be beneficial.
- the at least one corrosion inhibitor is preferably contained in a content of 0.005 to 2 wt .-% of the solids and active ingredients of the lubricant composition and / or the coating, particularly preferably from 0.1 to 1, 2 wt .-%.
- the lubricant composition may preferably each contain at least one surfactant, a defoamer, a leveling agent and / or a biocide. These additives are preferably each contained in a content of 0.005 to 0.8 wt .-% of the solids and active ingredients of the lubricant composition o- / / and the coating, particularly preferably from 0.01 to 0.3 wt .-%.
- a surfactant can serve as a leveling agent.
- At least one surfactant may in particular be a nonionic surfactant; this is preferably an ethoxylated fatty alcohol with 6 to 20 ethylene oxide groups.
- the at least one surfactant is preferably contained in a content of 0.01 to 2 wt .-%, particularly preferably from 0.05 to 1, 4 wt .-%.
- the addition of a defoamer may possibly be advantageous in order to brake the tendency to foam, which can be increased or caused in particular by an added surfactant.
- the lubricant composition may preferably contain at least one thickener, which belongs to the non-ionomers as a polymeric organic thickener and otherwise belongs not to the non-ionomers but to the additives.
- at least one primary or / and tertiary amine-containing compound a cellulose, a cellulose derivative, a silicate, such as e.g. one based on bentonite or / and at least one other phyllosilicate, a starch, a starch derivative and / or a sugar derivative.
- the lubricant composition and / or in the coating formed therefrom is preferably contained in the lubricant composition and / or in the coating formed therefrom in a content of 0.1 to 12 or from 1 to 6 wt .-% of the solids and active ingredients of the lubricant composition and / or the coating.
- At least one organic solvent or / and at least one solubilizer may also be added or contained in the lubricant composition.
- no or no higher contents (eg less than 0.5% by weight of the solid and active substances of the lubricant composition and / or the coating) of chlorine-containing compounds are present in the lubricant composition and / or in the coating formed therefrom
- Fluorine-containing compounds in particular fluorine-containing polymers / copolymers, compounds based on or containing isocyanate or / and isocyanurate, melamine resin, phenolic resin, polyethyleneimine, polyoxyethylene, polyvinyl acetate, polyvinyl alcohol, polyvinyl esters, polyvinyl pyrrolidone, more corrosive substances, to environmentally unfriendly and / or toxic heavy metal compounds, to borates, chromates, chromium oxides, other chromium compounds, molybdates, phosphates, polyphosphates, vanadates, tungstates, metal powders or / and to a soap commonly used in cold forming such as alkali metal and / or al
- the lubricant composition in many embodiments has a solids and active ingredient content preferably in the range of 2 to 95% by weight, in particular in the range of 3 to 85, 4 to 70 or 5 to 50, 10 to 40, 12 to 30 or 15 to 22 Wt .-%, wherein the remaining contents up to 100 wt .-% are either only water or predominantly water with contents of at least one organic solvent or / and at least one solubilizer.
- the aqueous lubricant composition is agitated prior to its application to the metallic surface.
- the aqueous lubricant composition When used as a so-called concentrate, the aqueous lubricant composition may have a solids and active substance content preferably in the range from 12 to 95, 20 to 85, 25 to 70 or 30 to 55% by weight, as application mixture ("bath") preferably in the range from 4 to 70, 5 to 50, 10 to 30 or 15 to 22 wt .-%. At low concentrations, the addition of at least one thickener may be advantageous.
- the metallic particles to be cold formed with the lubricant composition can preferably be wetted for a time of 0.1 second to 1 hour.
- the duration of wetting may depend on the type, shape and size of the metallic shaped bodies and depend on the desired layer thickness of the coating to be produced, for example, where long pipes are often introduced obliquely into the lubricant composition, so that the air can escape for a relatively long time, in particular inside the pipe.
- the application of the aqueous lubricant composition on the workpiece can be carried out with all methods customary in surface technology, for example by manual or / and automated application, by spraying or / and dipping and optionally additionally by squeezing and / or rolling, optionally in one flow dipping method.
- the cold-formed metallic molded body with the lubricant composition at a temperature preferably in the range of room temperature to 95 0 C, in particular at 50 to 75 0 C, wetted. If the temperature during wetting of the metallic shaped body is below 45 ° C., the drying usually proceeds without additional
- a coating of the lubricant composition is formed, the chemical composition of which does not have to match the starting composition and the phase content of the aqueous lubricant composition in every variant, but which largely or completely matches in many embodiments. In most embodiments hardly or no crosslinking reactions occur. For most or all of the embodiments involve drying of the aqueous lubricant composition on the metallic surface.
- the added substances are selected such that the softening / softening points and / or melting ranges / melting points of the individual polymeric constituents (monomers, monomers, oligomers, cooligomers, polymers and / or copolymers of the polymeric organic material), optionally also the waxes and distribute any additives that may be present over the temperature range, which is limited by the ambient or elevated temperature benchmarks in the range of 20, 50, 100, 150 or 200 ° C to 150, 200, 250, 300, 350 or 400 ° C.
- the friction in each temperature range, which is passed through the cold forming, facilitated by at least one softened and / or molten substance and thereby usually the cold forming is guaranteed.
- the coating produced with the lubricant compositions of the present invention is intended to facilitate cold working and thereafter be removed from the formed workpiece.
- the composition according to the invention may be designed so that the coating is particularly suitable for permanent retention on a formed workpiece, eg by using a content of at least one thermal crosslinking agent on at least one resin which is suitable for radical curing, for example UV curing, on at least one photoinitiator, for example for UV curing or / and on at least one film-forming auxiliary, in order to produce a particularly high-quality coating which is closed in many variants.
- the cured, crosslinked and / or post-crosslinked coatings can provide increased corrosion resistance and hardness compared to the coatings of the other embodiments.
- Particularly high-quality coatings for higher or the highest mechanical and / or thermal requirements have proven to be those in which the liquid, drying or / and dry coating which has been applied with the aqueous lubricant composition according to the invention up to temperatures of at least 200 0 C no stronger softening or / and only a limited softening or no softening until at least 300 0 C shows.
- the coating applied from the aqueous lubricant composition preferably has a coating weight in the range from 0.3 to 15 g / m 2 , in particular from 1 to 12, from 2 to 9 or from 3 to 6 g / m 2 .
- the layer The thickness of the coating is set in accordance with the conditions of use and may in particular be in a thickness in the range from 0.25 to 25 ⁇ m, preferably in the range from 0.5 to 20, from 1 to 15, from 2 to 10, from 3 to 8 or from 4 to 6 ⁇ m.
- the cold formed metallic moldings can basically consist of any metallic material. Preferably, they consist essentially of steel, aluminum, aluminum alloy, copper, copper alloy, magnesium alloy, titanium, titanium alloy, in particular mild steel, high-strength steel, stainless steel or / and metallically coated steel, e.g. aluminized or galvanized steel. In most cases, the workpiece consists essentially of steel.
- the metallic surfaces of the metallic workpieces to be cold formed and / or the surfaces of their metallized coating can be cleaned prior to wetting with the aqueous lubricant composition in at least one cleaning procedure, basically all cleaning methods are suitable for this purpose.
- the chemical and / or physical cleaning may include, above all, peeling, blasting, such as annealing, sandblasting, mechanical descaling, alkaline cleaning, and / or acid pickling.
- the chemical cleaning is carried out by degreasing with organic solvents, by cleaning with alkaline or / and acidic cleaners, with acid pickling or / and by rinsing with water.
- the pickling and / or blasting is used primarily for descaling the metallic surfaces.
- a welded tube made of cold strip after welding and scraping for example to pickle, rinse and neutralize a seamless tube or to degrease and, for example, to remove a stainless steel slug do the washing up.
- Parts made of stainless steel can be brought into contact both moist and dry with the lubricant composition, since rusting is not to be expected.
- the cold-formed metallic shaped bodies can be precoated with the lubricant composition according to the invention before wetting.
- the metallic surface of the workpiece may be provided, prior to wetting with the lubricant composition of the invention, with a metallic coating consisting essentially of a metal or metal alloy (e.g., aluminized or galvanized).
- the metallic surface of the workpiece or its metallically coated coating can be provided with a conversion coating, in particular oxalated or phosphated.
- the conversion coating may preferably be treated with an aqueous composition based on oxalate, alkali phosphate, calcium phosphate, magnesium phosphate, manganese phosphate, zinc phosphate or corresponding mixed crystal phosphate, such as e.g. ZnCa phosphate.
- the metallic moldings are also blank, that is wetted without a previous conversion coating, with the lubricant composition of the invention. The latter is only possible if the metallic surface of the workpiece to be formed is previously cleaned chemically and / or physically.
- the metallic mold bodies are preferably thoroughly dried after coating with the lubricant composition, in particular with warm air and / or radiant heat. This is often necessary because, as a rule, water contents in coatings interfere with cold forming, because otherwise the coating can be insufficiently formed and / or because a coating of inferior quality can be formed. This can also occur quickly Anrosten.
- the coating according to the invention with sufficient drying of such good quality that they with careful handling of the metallic coated molding is not damaged and is not partially removed.
- the metallic moldings coated in accordance with the invention can be used for cold forming, in particular for sliding, e.g. of tubes, hollow sections, bars, other solid sections and / or wires, for ironing and / or deep drawing, e.g. of tapes, sheets or / and hollow bodies, e.g. to hollow bodies, for cold extrusion e.g. hollow bodies and / or solid bodies and / or for cold heading, e.g. from wire sections to connectors such as e.g. to bolts and / or screw blanks, sometimes also several, possibly even different, cold forming operations can be performed sequentially.
- the formed workpiece can preferably be at least partially cleaned of the remaining coating or / and the deposits of the lubricant composition.
- the coating on the reshaped workpieces may, if necessary after cold forming, remain at least partially permanent.
- the object is also achieved with a lubricant composition according to the invention for application to a workpiece to be formed and for cold forming.
- the object is also achieved with a coating which has been formed from a lubricant composition according to the invention.
- a lubricant composition according to the invention for application to a workpiece to be formed and for cold forming and to the use of a coating according to the invention for cold forming and optionally also as a durable protective coating. It has surprisingly been found that even a very small addition of a water-soluble, water-containing or / and water-binding oxide o- / silicate, especially of water glass, but also a high addition leads to a significant improvement of the coating according to the invention, which leads to a significantly improved cold working under otherwise identical conditions and can be used in more severe cold forming than comparable, free of these compounds lubricant compositions.
- the coating according to the invention can also be used for cold forming at higher force and at higher temperature without the addition of solid lubricants and without applying a separate solid lubricant layer as comparable Ü- coatings without this addition. Furthermore, this addition also has a significant anti-corrosive effect.
- the cold extrusion - especially of steel scraps - according to the invention particularly low friction and especially without breakage of the tool even when using significantly increased forces.
- it is possible to produce coatings both in the range of extreme pressing pressures, as well as in the area of maximum wear minimization during cold forming, increased molding accuracy and / or increased forming speed. can be applied simply, reproducibly and inexpensively by dipping, pulling out and drying.
- compositions (A) were prepared with an amine alcohol, which were initially kept at temperatures in the range of 80 to 95 0 C, on the other hand compositions (B) were set with an ammonium content, the entire duration in space temperature and / and held at up to 30 0 C.
- Lubricant concentrates and baths were basically the same procedure.
- the at least one ionomer based on ethylene acrylate was added to the initially introduced water, partly as a dispersion.
- the mixture (A) was further maintained at temperatures in the range of 80 to 95 0 C and further stirred vigorously with a dissolver to allow the neutralization and salt formation. This resulted in a transparent liquid after some time.
- the at least one ionomer based on ethylene acrylate in the form of at least one dispersion of at least one organic ammonium salt was added and further stirred vigorously with a dissolver.
- the non-ionomers were added first in dissolved and / or dispersed form and then in powder form with vigorous and long-term stirring with a dissolver.
- the temperature was lowered again to the range from 60 to 70 ° C.
- further additives such as biocide, wetting agent and corrosion inhibitor and finally at least one thickener for adjusting the viscosity were added as needed.
- the respective concentrate was filtered and the pH was adjusted.
- the respective concentrate was diluted appropriately with demineralized water and, if necessary, the pH was adjusted.
- the baths with the aqueous lubricant composition were stirred gently over time and kept at a temperature in the range of 50 to 70 0 C (bath A) or 15 to 30 0 C (bath B).
- the coating of the phosphated slugs with the polymeric and mostly aqueous lubricant composition according to the invention was carried out by dipping for 1 min and then drying for 10 min at 60 to 65 0 C in a convection oven. These doubly coated dried slugs were then cold worked in a press by backward extrusion at 300 tons.
- Tables 1 and 2 give the lubricant compositions and the suitability of the coatings formed therewith on ZnCa phosphate coatings for certain cold forming operations and their degree of deformation. The remainder to 100 wt .-% form the additives and solid lubricants, only the latter are given.
- the ionomers used are ethylene acrylates and / or ethylene methacrylates ("ethylene acrylate").
- Ammonium polymer refers to organic polymeric ammonium salts of non-ionomers which have been added as dispersions.
- Table 2 shows a variety of basic compositions having a varying content of waterglass.
- the additives only the solid lubricants are given, which is why the sum of the solids and active ingredients does not give 100 wt .-%.
- Type A and C ionomers have a slightly higher molecular weight and significantly higher melt viscosity (high temperature viscosity especially in the softening and / or melting) than the B and D type ionomers.
- Types A and B ionomers were included the preparation of the aqueous lubricant composition with an amine alcohol.
- the ionomers of types C and D have an ammonium content and have already been added as organic salts.
- Table 1 Compositions of the aqueous lubricant compositions with data in wt .-% of the solids and active ingredients and the suitability of the coatings formed therewith on ZnCa-phosphate coatings for certain cold forming operations and their degree of deformation for different types and amounts of water-soluble, hydrous or / and water-binding oxide and / or silicate such as water glass
- Table 2 Compositions of the aqueous lubricant compositions with details in wt .-% of the solids and active ingredients and the suitability of the coatings formed therewith on ZnCa-phosphate coatings for certain cold forming operations and their degree of deformation for a variety of basic compositions with a varying content of water glass with to the right increasing degree of deformation
- the tests in Table 2 showed that the content of the lubricant compositions according to the invention can be varied to a large extent on various components.
- the addition of at least one ionomer and water glass, but also of at least two waxes with graduated melting temperatures has proven particularly useful.
- the lubricant composition and the coating formed therefrom are more or better usable for severe forming if a higher content of ionomer (s) or an additional high content of at least one solid lubricant is included.
- the lubricant compositions of Examples 19 and 20 are particularly suitable for heavy cold working such as tumble pressing due to the content of graphite or molybdenum disulfide.
- the Schmierstoffzusannnnenianaen invention allow environmentally friendly coatings that are applied to metallic workpieces in a simple and cost-effective manner and suitable for simple, medium or heavy heavy cold and / or. Due to the use of organic salts, the coatings and corresponding deposits can be easily removed after cold working from the formed workpiece.
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Abstract
Description
Claims
Priority Applications (13)
Application Number | Priority Date | Filing Date | Title |
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BRPI0906445-1A BRPI0906445B1 (pt) | 2008-01-30 | 2009-01-26 | Processo para a preparação de peças metálicas em bruto para modelar a frio através da aplicação de uma camada de lubrificante, composição lubrificante e revestimento |
CN200980111861.4A CN101983233B (zh) | 2008-01-30 | 2009-01-26 | 用润滑剂组合物涂覆金属表面的方法 |
AU2009209699A AU2009209699B2 (en) | 2008-01-30 | 2009-01-26 | Method for coating metal surfaces with a lubricant composition |
RU2010135775/04A RU2535666C2 (ru) | 2008-01-30 | 2009-01-26 | Способ покрытия металлических поверхностей композицией смазочных материалов |
US12/863,828 US8915108B2 (en) | 2008-01-30 | 2009-01-26 | Method for coating metal surfaces with a lubricant composition |
DK09706791.2T DK2238228T3 (da) | 2008-01-30 | 2009-01-26 | Fremgangsmåde til belægning af metaloverflader med en smøremiddelsammensætning |
EP09706791.2A EP2238228B1 (de) | 2008-01-30 | 2009-01-26 | Verfahren zur beschichtung von metallischen oberflächen mit einer schmierstoffzusammensetzung |
UAA201010444A UA103312C2 (ru) | 2008-01-30 | 2009-01-26 | Способ нанесения на металические поверхности смазочной композиции |
ES09706791.2T ES2523589T3 (es) | 2008-01-30 | 2009-01-26 | Procedimiento para el revestimiento de superficies metálicas con una composición de material lubricante |
MX2010008373A MX2010008373A (es) | 2008-01-30 | 2009-01-26 | Un proceso para el revestimiento de superficies metalicas con una composicion lubricante. |
PL09706791T PL2238228T3 (pl) | 2008-01-30 | 2009-01-26 | Sposób powlekania powierzchni metalowych za pomocą kompozycji środka smarnego |
CA2713543A CA2713543C (en) | 2008-01-30 | 2009-01-26 | A process for the coating of metallic surfaces with a lubricant composition |
ZA2010/05733A ZA201005733B (en) | 2008-01-30 | 2010-08-11 | A process for the coating of metallic surfaces with a lubricant composition |
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DE102008000185.6 | 2008-01-30 | ||
DE102008000185 | 2008-01-30 |
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Country Status (20)
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US (1) | US8915108B2 (de) |
EP (1) | EP2238228B1 (de) |
KR (1) | KR101653782B1 (de) |
CN (1) | CN101983233B (de) |
AR (1) | AR070688A1 (de) |
AU (1) | AU2009209699B2 (de) |
BR (1) | BRPI0906445B1 (de) |
CA (1) | CA2713543C (de) |
CL (1) | CL2009000225A1 (de) |
DK (1) | DK2238228T3 (de) |
ES (1) | ES2523589T3 (de) |
HU (1) | HUE026557T2 (de) |
MX (1) | MX2010008373A (de) |
PL (1) | PL2238228T3 (de) |
PT (1) | PT2238228E (de) |
RU (1) | RU2535666C2 (de) |
TW (1) | TWI457431B (de) |
UA (1) | UA103312C2 (de) |
WO (1) | WO2009095375A1 (de) |
ZA (1) | ZA201005733B (de) |
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Cited By (5)
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WO2021170706A1 (en) | 2020-02-25 | 2021-09-02 | Chemetall Gmbh | One-step pretreatment method of metallic substrates for metal cold forming |
WO2021170707A1 (en) | 2020-02-25 | 2021-09-02 | Chemetall Gmbh | One-step pretreatment method of metallic substrates for metal cold forming |
WO2022207901A1 (en) | 2021-04-01 | 2022-10-06 | Chemetall Gmbh | One-step pretreatment method of metallic substrates at non-neutral ph values for metal cold forming |
CN115386410A (zh) * | 2022-08-11 | 2022-11-25 | 西安建筑科技大学 | 一种钛合金挤压用高温固体润滑剂及其制备方法 |
CN115386410B (zh) * | 2022-08-11 | 2023-09-12 | 西安建筑科技大学 | 一种钛合金挤压用高温固体润滑剂及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CA2713543A1 (en) | 2009-08-06 |
PT2238228E (pt) | 2014-10-15 |
CN101983233B (zh) | 2015-02-11 |
EP2238228A1 (de) | 2010-10-13 |
RU2010135775A (ru) | 2012-03-10 |
DK2238228T3 (da) | 2014-09-29 |
KR101653782B1 (ko) | 2016-09-05 |
TWI457431B (zh) | 2014-10-21 |
AU2009209699A1 (en) | 2009-08-06 |
HUE026557T2 (hu) | 2016-06-28 |
PL2238228T3 (pl) | 2015-02-27 |
UA103312C2 (ru) | 2013-10-10 |
BRPI0906445A2 (pt) | 2021-05-11 |
CA2713543C (en) | 2016-12-13 |
CN101983233A (zh) | 2011-03-02 |
RU2535666C2 (ru) | 2014-12-20 |
BRPI0906445B1 (pt) | 2022-01-11 |
CL2009000225A1 (es) | 2010-10-15 |
MX2010008373A (es) | 2010-08-23 |
TW200932894A (en) | 2009-08-01 |
EP2238228B1 (de) | 2014-06-18 |
AR070688A1 (es) | 2010-04-28 |
ES2523589T3 (es) | 2014-11-27 |
ZA201005733B (en) | 2011-10-26 |
KR20100112635A (ko) | 2010-10-19 |
US8915108B2 (en) | 2014-12-23 |
US20110048090A1 (en) | 2011-03-03 |
AU2009209699B2 (en) | 2013-01-17 |
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