EP3058116B1 - Verfahren zur vorbereitung von metallischen formkörpern für die kaltumformung - Google Patents

Verfahren zur vorbereitung von metallischen formkörpern für die kaltumformung Download PDF

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EP3058116B1
EP3058116B1 EP14784475.7A EP14784475A EP3058116B1 EP 3058116 B1 EP3058116 B1 EP 3058116B1 EP 14784475 A EP14784475 A EP 14784475A EP 3058116 B1 EP3058116 B1 EP 3058116B1
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Prior art keywords
layer
oxalate
bath
oxalic acid
range
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German (de)
English (en)
French (fr)
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EP3058116A1 (de
Inventor
Benjamin GÜTTLER
Ralf Schneider
Frank Hollmann
Gorka DE LUIS GARCIA
Iñaki NIEVES QUINTANA
Martin ORBEN
Norbert Schwinke-Kruse
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Chemetall GmbH
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Chemetall GmbH
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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
    • C23C22/46—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
    • 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
    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06—Zinc or cadmium or alloys based thereon
    • 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
    • C23C22/78—Pretreatment of the material to be coated
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • 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

Definitions

  • the invention relates to a method as specified in claim 1 for coating metallic moldings first with an aqueous acidic oxalation solution and then with a lubricant composition in the form of an aqueous solution or dispersion based on organic polymer / copolymer to prepare the metallic moldings for cold forming.
  • Cold forming can usually take place at surface temperatures of up to around 450 ° C without external heat input.
  • the heating can occur solely through the frictional forces acting during the forming process between the coated metallic shaped body blank and the tool and through internal frictional forces due to the flow of material, but possibly also through preheating of the shaped body to be formed.
  • the temperature of the shaped bodies to be reshaped is often initially around ambient temperature, that is to say about 10 to 32.degree.
  • the shaped bodies to be reshaped are preheated to temperatures, for example, in the range from 650 to 850 ° C., from 850 to 1250 ° C. or from 650 to 1250 ° C., one speaks of warm forging or forging.
  • increased to high pressures usually occur during cold forming, e.g. for steel in the range from 200 MPa to 1 GPa and sometimes even up to 2 GPa.
  • the shaped bodies to be formed are mostly strips, sheets, slugs, wires, wire coils, more complex shaped parts, sleeves, profiles such as hollow or solid profiles, tubes, circular blanks, disks, rods, rods and / or cylinders.
  • a slug is a disk or a section of wire, wire bundle or rod.
  • the metallic moldings to be cold formed can in principle consist of any metallic material. They preferably consist essentially of steel, aluminum, aluminum alloy, copper, copper alloy, magnesium alloy, titanium, titanium alloy, in particular of structural steel, high-strength steel, stainless steel, iron or steel material with a chromium content and / or metallic coated steel such as aluminized or galvanized steel. Most of the time, the shaped body consists essentially of steel.
  • the metallic moldings for cold forming were almost exclusively prepared for cold forming either by applying a fat, an oil or an oil emulsion.
  • a separating layer has usually been followed by a layer of lubricant in order to minimize the friction that occurs during the forming process.
  • the blanks are usually first coated with zinc phosphate to form a separating layer and then either with a soap, in particular based on alkali or / and alkaline earth stearate or / and with a solid lubricant, in particular based on molybdenum sulfide and / and carbon, to form a lubricant layer before the blanks coated in this way are cold-formed.
  • the metallic moldings to be cold formed are precoated before cold forming.
  • the metallic surface of the molded body or its metallic coated coating can be provided with a conversion coating, in particular oxalated or phosphated.
  • the conversion coating can preferably be carried out with an aqueous composition based on oxalate, alkali phosphate, calcium phosphate, magnesium phosphate, manganese phosphate, zinc phosphate or a corresponding mixed crystal phosphate such as ZnCa phosphate.
  • the metallic moldings are also bare, that is, wetted with a lubricant composition without a previous conversion coating. The latter is only possible if the metallic surface of the shaped body to be reshaped is cleaned chemically and / or physically beforehand.
  • any of the pamphlets US 3481762 A , DE 2125503 A1 and US 2850417 A each discloses an oxalate coating on a steel surface prior to forming.
  • the steels which can be used according to the invention are characterized as those which have a carbon content in the range from 0 to 2.06% by weight and therefore do not belong to the iron materials, and as those which have a chromium content in the range from 0 to ⁇ 10% by weight and in particular in the range from 0.01 to 9% by weight, from 0.05 to 8% by weight, from 0.1 to 7, from 0.2 to 5% by weight. -%, from 0.25 to 4% by weight or from 0.3 to 2.5% by weight.
  • Steels have a carbon content in the range from 0 to 2.06% by weight.
  • the chromium content of the steel in particular influences the pickling attack of an acidic aqueous oxalation composition and also of an acidic aqueous zinc phosphating composition. Because if the chromium content is well above 10% by weight, a passivating layer forms on the steel surface, which protects the steel from oxidation and chemical attack. Then, however, the pickling attack on the substrate is inhibited or completely prevented, and a separating layer does not form because no iron can be dissolved out of the substrate.
  • aqueous oxalating compositions with a content resulted, for example an extremely strong pickling attack on thiosulphate and / or on halogen compounds, so that no adequate separating layers, namely too thin and not closed, or no separating layers at all were formed. These oxalate layers were completely unsuitable for cold forming.
  • aqueous oxalation compositions containing, for example, thiosulphate and / or halogen compound resulted in an advantageous pickling attack, which also resulted in the high chromium content of these formed passivating layer attacks, so that good oxalate layers were formed due to the very strong pickling attack.
  • oxalate layers were also well suited for cold forming.
  • the table shows the strong dependency of cold formability and the quality of cold forming on the presence and quality of the oxalate layer.
  • Gardomer® based on organic polymer / copolymer was used for the lubricant layer, which is ideally suited for cold forming as a lubricant layer and has a very wide range of performance.
  • the ratio of pickling attack to layer weight is much too high, so that particularly thin oxalate layers were formed which did not result in any closed or adherent layers.
  • the passivating layer on the high-chromium steel is not attacked, so that no pickling takes place, so that no pickling takes place and the formation of an oxalate layer does not occur.
  • the pickling attack is so strong that it removes the passivating layer on the high-chromium steel, so that the pickling removal, the layer weight and the ratio of BA to SG are of a suitable strength; as a result, a good oxalate layer is formed, which enables good cold forming.
  • phosphating is still the usual treatment for forming a separating layer.
  • phosphating has the considerable disadvantage that they contain phosphate. This is because phosphorus diffuses from the metallic surface into the steel structure during heat treatment, and the phosphorus content damages the properties of these Steels, especially through delta ferrite formation, sensitivity to impact stress and embrittlement. Phosphorus-induced embrittlement renders critical components unusable, as notched impact strength, brittleness, etc. are impaired.
  • DE 976692 B teaches the use of oxalating solutions with a content of 1 to 200 g / L oxalic acid, 0.2 to 50 g / L iron chlorides, 5 to 50 g / L phosphate calculated as P 2 O 5 and optionally Cr or Ni Salt.
  • U.S. 2,550,660 describes the addition of oxygen-containing sulfur compounds such as sodium thiosulphate and halogen compounds such as sodium chloride and ammonium bifluoride, which increase the attack of oxalic acid solutions on stainless steels and therefore form oxalate layers with lower levels of activators.
  • oxygen-containing sulfur compounds such as sodium thiosulphate and halogen compounds such as sodium chloride and ammonium bifluoride
  • Oxalating metallic surfaces is also known for the purpose of corrosion protection and, if necessary, also to improve paint adhesion.
  • the oxalate layers In comparison to zinc phosphate layers, however, due to the halide content, the oxalate layers have proven to be so little anti-corrosive and so poorly adherent that oxalate has practically not been used for the purpose of corrosion protection for decades. The only exception is for the formation of the separating layer for the cold forming of corrosion-resistant steels with significantly more than 10% by weight of chromium.
  • Oxalating enables the formation of a completely phosphate-free separating layer without the use of environmentally unfriendly heavy metals.
  • Iron and zinc are not considered environmentally unfriendly for the purposes of this application Considered cations or heavy metals. Iron and zinc compounds are not regarded as environmentally unfriendly heavy metal compounds for the purposes of this application.
  • the use of oxalation according to the prior art due to the halogen and / or sulfur compounds used on non-corrosion-resistant steels with a chromium content of less than 10% by weight, leads to undesired corrosion and to very poorly adhering layers that are not suitable for cold forming are suitable because they do not have a separating layer that works reliably during cold forming.
  • the object was to propose a method for treating molded bodies with an iron or steel surface with a chromium content in the range from 0 to ⁇ 10% by weight in a conversion treatment prior to cold forming, in which the process is essentially phosphate-free or entirely phosphate-free and in which the addition of environmentally unfriendly heavy metals can be dispensed with.
  • a strip, sheet metal, slug, wire, wire collar, more complex shaped molded part, a sleeve, a profile, tube, a round blank, disk, rod, a rod and / or cylinder made of a steel material before cold forming is used as the substrate is / is oxalated.
  • the substrate can optionally have a zinc or zinc alloy layer.
  • a zinc or zinc alloy layer usually only slugs are galvanized or alloyed.
  • the blanks to be formed are first heat-treated to adjust the material properties, e.g. by soft annealing, so that they can be easily cold-formed.
  • the surfaces of the blanks to be cold formed and / or the surfaces of their metal-coated coating can be used before wetting be cleaned with the aqueous oxalation composition in at least one cleaning process, in principle all cleaning processes are suitable for this purpose.
  • the chemical and / or physical cleaning can primarily include mechanical descaling, annealing, peeling, blasting such as sandblasting, in particular alkaline cleaning and / and acidic pickling.
  • Chemical cleaning is preferably carried out by degreasing with organic solvents, by cleaning with alkaline and / or acidic cleaners, with neutral cleaners, with acidic stains and / and by rinsing with water.
  • Pickling and / or blasting is mainly used for descaling the metallic surfaces.
  • At least one strong acid-resistant surfactant such as, in particular, at least one cationic surfactant such as a laurylamine polyethylene glycol ether such as Marlazin® L 10 or / and a benzalkonium chloride such as Lutensit® TC-KLC 50 der Oxalating composition according to the invention is / is added, so that at least something is also cleaned during oxalating and / or cleaning and oxalating takes place in a one-pot process. The separate cleaning step can then be omitted for less soiled parts.
  • the addition of surfactants in the oxalating bath also has the advantages that it can be cleaned and oxalated in a single bath and in a single process step, that the metallic surface is attacked more evenly by the oxalic acid and can be coated better and more evenly with the oxalate layer and that the accumulation of sludge particles on the oxalate layer can be prevented more effectively.
  • compositions that “consist essentially of” certain components can also “consist” only of these components or “contain” these components.
  • the aqueous conversion layer can optionally be separated or only dried together with the subsequently applied lubricant layer, wherein the conversion layer can contain a residual water content when the lubricant layer is applied in the latter variant in order to avoid a drying step and / or to make the lubricant layer sufficiently adhesive and still apply moist conversion layer. It is particularly preferred here that the oxalated substrates are coated with a layer of lubricant in the wet-on-wet process.
  • the bath may contain iron, zinc, steel finishing elements and / or alloy components and possibly also small amounts of halogen compounds, phosphorus compounds and / or sulfur compounds from other baths and parts of the system in order to form the separating layer introduced into the bath to form the separating layer at least from time to time in some systems.
  • Water is used as the solvent, in particular as deionized water or as city water.
  • the water content of the aqueous oxalating composition is preferably 40 to 99.75% by weight of water.
  • This composition and / or the bath will be / are only prepared with a mixture that essentially consists of water, 2 to 500 g / L oxalic acid, calculated as anhydrous oxalic acid and a) 0.01 to 20 g / L of at least one accelerator based on guanidine, calculated as nitroguanidine or / and b) 0.01 to 20 g / L of at least one nitrate calculated as sodium nitrate and optionally at least one thickening agent based on at least one compound of polyacrylamide, polyallylamine, polyethylene glycol, polysaccharide, polysiloxane, polyvinylamide and / or polyvinylamine in a content im Range from 0.01 to 50 g / L, optionally from a pigment for the flowability of oxalic
  • a supplement is added if necessary, which essentially consists of only or only at least one of the components of the batch.
  • Oxalic acid is usually the most consumed here and should therefore usually be added first.
  • water does not necessarily have to be added.
  • the oxalic acid is calculated as completely dissolved oxalic acid, since g / L is used as the unit.
  • the oxalic acid is usually contained in water and in the entire bath in a stable manner up to the solubility limit at the respective temperature.
  • Commercially available oxalic acid is often in the form of a coarse powder and may then need to be finely ground before it is added to the bath.
  • a finely divided powder such as an oxidic or silicate powder, in particular with an average powder particle size in the range from 0.5 to 20 ⁇ m
  • the free-flowing oxalic acid has the advantage that the oxalic acid does not cake and is therefore easier to handle.
  • the flowability is of great importance for the pumpability and dosability of the powder.
  • the pourability ensures that a suitable fine-grain pigment surrounds the components and in particular the oxalic acid and prevents neighboring powder particles from growing together. As a result, clumping of oxalic acid is significantly reduced or completely prevented. Lumpy products cannot be dosed and in some cases cannot be used with automatic suction systems. Furthermore, the disintegration times of lumpy products are much greater.
  • the aqueous composition can contain 0.001 to 20 g / l of at least one inorganic or organic pigment, preferably pigment based on oxide, organic polymer and / or wax. Titanium oxide powders in particular have proven particularly useful.
  • oxalic acid contents in the range from 0.5 to 400 g / L can be used well for oxalating.
  • particularly high contents of oxalic acid are only found dissolved in water at high temperatures.
  • contents of the order of magnitude of 1 g / L however, the oxalic acid content of the aqueous composition must be supplemented after a very short time and often.
  • the aqueous acidic composition according to the invention for forming a conversion layer and / or the bath preferably have an oxalic acid content in the range from 5 to 400 g / L, from 10 to 300 g / L, from 15 to 200 g / L, from 20 to 120 g / L, from 25 to 90 g / L, from 30 to 60 g / L or from 35 to 40 g / L, calculated as anhydrous oxalic acid C 2 H 2 O 4 .
  • the dilution factor of a concentrate containing oxalic acid to the bath can preferably be in the range from 1 to 20, diluting with water.
  • iron oxalate, iron oxalate dihydrate, zinc oxalate and / or zinc oxalate dihydrate are formed from the oxalate due to the pickled metal ions.
  • At least one accelerator based on guanidine and / or at least one nitrate including nitric acid, calculated as NO 3 can be used as the accelerator. Beyond this, further accelerators are not necessary and often also not useful. Nitrite as an accelerator is unstable as an accelerator in the presence of iron oxalate and forms disruptive nitrous gases. As an accelerator, chlorate contains halogens. An m-nitrobenzenesulfonate such as the sodium salt SNBS contains sulfur as an accelerator. Hydrogen peroxide reacts chemically with oxalic acid and does not act as an accelerator. Hydroxylamine compounds as accelerators are suspected of forming carcinogenic nitrosamines. Thiosulfates as accelerators cause a far too strong pickling attack, so that no oxalate layer is formed as a result.
  • Acetatoguanidine, aminoguanidine, carbonatoguanidine, iminoguanidine, melanilinoguanidine, nitroguanidine, nitroguanidine and / or ureidoguanidine, for example, can be added as accelerators a) based on guanidine.
  • Aminoguanidine and nitroguanidine are particularly preferred here.
  • nitroguanidine can preferably also contain a stabilizer, such as a content as silicate, to reduce the impact sensitivity. Due to a low concentration of nitroguanidine in the aqueous composition and possibly also an addition of a stabilizer, an over-rapid reaction of the nitroguanidine is reliably avoided.
  • This stabilizer preferably also acts as a biocide and / or as a thickener.
  • Sodium nitrate, potassium nitrate, ammonium nitrate, nitric acid and many other organic and / or inorganic nitrates such as iron nitrate can be used as accelerators based on nitrate.
  • sodium nitrate, potassium nitrate and nitric acid are particularly preferred.
  • guanidine compound is used as an accelerator, a slightly increased consumption of this accelerator can often be observed. If only nitrate is used as an accelerator, then a slightly higher concentration of this accelerator should be selected. If at least one If guanidine compound and at least one nitrate are used as accelerators, then a significantly lower consumption of guanidine compound and at the same time a somewhat lower consumption of nitrate can often be observed.
  • the aqueous acidic composition according to the invention for forming a conversion layer and / or the bath preferably have a total content of accelerators a) and / or b) in the range from 0.05 to 30 g / L, from 0.1 to 20 g / L, of 0.2 to 12 g / L, from 0.25 to 10 g / L, from 0.3 to 8 g / L, from 0.35 to 6 g / L, from 0.4 to 4 g / L, from 0.45 to 3 g / L or from 0.5 to 2 g / L, calculated as the sum of the calculated contents based on nitroguanidine and sodium nitrate.
  • the aqueous acidic composition according to the invention for forming a conversion layer and / or the bath preferably have a content of guanidine-containing accelerators a) in the range from 0.05 to 18 g / L, from 0.1 to 15 g / L, from 0, 2 to 12 g / L, from 0.3 to 10 g / L, from 0.4 to 8 g / L, from 0.5 to 6 g / L, from 0.6 to 5 g / L, from 0, 7 to 4 g / L, from 0.8 to 3 g / L, from 0.9 to 2.5 g / L or from 1 to 2 g / L, calculated as nitroguanidine CH 4 N 4 O 2 .
  • the aqueous acidic composition according to the invention for forming a conversion layer and / or the bath preferably have a total content of nitrate-containing accelerators b) in the range from 0.05 to 18 g / L, from 0.1 to 15 g / L, from 0, 2 to 12 g / L, from 0.25 to 10 g / L, from 0.3 to 8 g / L, from 0.35 to 6 g / L, from 0.4 to 4 g / L, from 0, 45 to 3 g / L or from 0.5 to 2 g / L, calculated as sodium nitrate NaNO 3 .
  • the ratio of the concentrations in g / L of oxalic acid calculated as anhydrous oxalic acid to the total of the accelerators a) and b) calculated as nitroguanidine and / or sodium nitrate, of which at least one accelerator is present, in the aqueous acidic composition to form a conversion layer or / and the bath is preferably in the range from 500: 1 to 2: 1, from 150: 1 to 5: 1, from 80: 1 to 8: 1, from 40: 1 to 10: 1 or from 20: 1 to 12: 1.
  • a thickener can help to adjust the viscosity of the bath, influence the formation of the wet film and reduce the corrosion of the surfaces of the blanks. If no thickener is used, the formation of the wet film can be significantly less than with a thickener and the drying of the wet film can take place more quickly than with a thickener. If the content of a thickener in the bathroom is too high, the wet film may only dry very slowly.
  • the thickener should be stable in the bath.
  • the thickening agent can be added both in the batch and during operation of the bath.
  • the at least one thickener is used to set a viscosity of the bath in the range from 0.2 to 5 mPa.s measured at 20 ° C. with a rotary viscometer.
  • the thickener according to the invention is preferably a polysaccharide such as, for example, based on cellulose or xanthan and / or a polyethylene glycol, in particular a polyethylene glycol with an average molecular weight in the range from 50 to 2000 or from 200 to 700.
  • the at least one thickener is preferably used in a content of 0 or in the range from 0.01 to 50 g / L in the aqueous acidic composition according to the invention to form a conversion layer and / or in the bath, particularly preferably in a content in the range of 0, 1 to 50 g / L, from 1 to 45 g / L, from 2 to 40 g / L, from 3 to 30 g / L, from 4 to 25 g / L or from 5 to 20 g / L, calculated as completely dissolved active ingredient or as completely dissolved thickening agent in the bath.
  • the treatment bath can be made up with a liquid aqueous concentrate which is produced by dissolving a predetermined amount of oxalic acid and, if necessary, also by adding accelerator, pigment, surfactant and / and thickening agent in deionized water.
  • the dilution factor for diluting a concentrate to make a bath can be kept in the range from 1 to 100.
  • the treatment bath can be made up with a powdery concentrate, which is produced by kneading, rubbing, mixing in and / or rubbing in powdery oxalic acid and optionally with the addition of nitrate dissolved in water, pigment for increasing the flowability, surfactant and / or thickener, for example in a kneader and / or mixer is produced.
  • the factor for the dissolution of the concentrate in water for the bath formulation can be kept in the range from 1 to 100.
  • the treatment bath can be made up with a pasty concentrate, which is prepared by mixing oxalic acid with water and optionally with the addition of at least one accelerator dissolved in water, pigment for increasing the flowability, surfactant and / and thickening agent, for example in a kneader or / and mixer is made. It can have a water content of up to about 10% by weight.
  • This concentrate can be adjusted to a paste-like, meterable and easily dissolvable product.
  • the dilution factor for the dilution of this concentrate to the bath formulation can be kept in the range from 1 to 100.
  • the powdery concentrates are particularly advantageous in manufacture and transport.
  • the highly concentrated paste has the advantage of being one-component and easy to use.
  • the pH of the aqueous acidic composition for forming the conversion layer is usually in the range from 0 to 3 or from 0.2 to 2.
  • the aqueous acidic bath composition for forming a conversion layer as a separating layer, the oxalate bath preferably has a total acid GS in the range from 3 to 870 points.
  • the total acid is measured as follows:
  • the acids are oxalic acid and optionally nitric acid. It is determined by the consumption of 0.1 molar sodium hydroxide solution using the indicator phenolphthalein in 10 ml of oxalating composition diluted with 50 ml of deionized water. This consumption of 0.1 M NaOH in ml corresponds to the number of points for the total acid. If a further acid occurs in addition to oxalic acid in the oxalation composition, the content of the further acid can be determined separately and deducted from the total acid determined in order to obtain the value GS based only on the oxalic acid.
  • the content of total acid can preferably be in the range from 3 to 900 points, from 8 to 800 points, from 12 to 600 points, from 20 to 400 points, from 30 to 200 points, 40 to 100 points or 50 to 70 points.
  • the contact time of a metallic surface of a blank during dipping is preferably in the range from 0.5 to 30 minutes, in particular in the range from 1 to 20 minutes, from 1.5 to 15 minutes, from 2 to 10 minutes or from 3 to 5 minutes.
  • the contact time of a metallic surface of a blank during spraying is preferably in the range from 1 to 90 s, in particular in the range from 5 to 60 s or from 10 to 30 s.
  • the blanks are contacted with the oxalation composition by sprinkling, spraying and / or dipping at a temperature of 10 to 90 ° C.
  • the bath temperature of the oxalate bath is in the range from 10 to 90.degree. C., in particular in the range from 25 to 80.degree. C., from 40 to 70.degree. C. or from 50 to 65.degree.
  • the pickling removal BA is in the range from 1 to 6 g / m 2 , preferably in the range from 1.3 to 4.5 g / m 2 or from 1.5 to 3 g / m 2 . It is determined by weighing dried coated substrates before and after coating. Here it may be desirable to set as little pickling removal as possible in order to generate as little sludge as possible, in particular based on iron oxalate, which has to be disposed of. On the other hand, it can be advantageous to adjust the pickling rate on the substrate and the system conditions so that, among other things, light scale residues are also removed from the substrate.
  • the aqueous solution or dispersion of the bath prepared with the batch and optionally also with at least one supplement is preferably largely or completely free of heavy metals from the added components, largely or completely halogen-free, largely or completely sulfur-free and largely or completely phosphate-free, but can occasionally contain up to about 0.001 g / L PO 4.
  • undesirable contents in small quantities or traces, in particular of halogen, phosphorus, sulfur and / and in particular environmentally unfriendly heavy metal compounds, especially from previous ones Baths, pipes and other system parts are dragged in.
  • the steel surfaces are coated with the oxalating composition according to the invention
  • some of the chemical elements of the steel surface are pickled out and incorporated into the aqueous solution or dispersion.
  • This can therefore accumulate with iron and other elements such as the steel finishing elements and other alloy elements such as chromium, nickel, cobalt, copper, manganese, molybdenum, niobium, vanadium, tungsten and zinc and / or their ions in the bath over time.
  • these elements or ions do not form precipitation products that sink and form sludge, but instead precipitate as oxalates.
  • the precipitated oxalates and oxalate dihydrates form a sludge that is easily removable and, compared to phosphates, environmentally friendly. Some of these elements or ions, like some of the additives and impurities in the bath, are built into the oxalate layer.
  • the bath can therefore absorb an iron content of up to 0.5 g / L or even up to around 1 g / L over a longer period of time.
  • the bath composition for oxalating and / or the oxalate layer consists essentially only of oxalic acid, guanidine compound, nitrate and / or their derivatives and optionally of pigment, surfactant and / or thickener and is / are largely or completely free of halogen Compounds, phosphorus compounds, sulfur compounds and / or heavy metals other than iron and zinc.
  • the oxalate layer produced with the method according to the invention can, if necessary, be dried, can optionally dry slightly or also be coated further while wet. In the case of drying, for example, drying with hot air at a temperature in the range from 80 to 120 ° C is recommended.
  • the oxalated substrates which may also be coated with a lubricant layer, are cold-formed, in particular, by slide drawing such as wire drawing or pipe drawing, by cold forging, ironing, ironing, deep drawing, cold extrusion, thread rolling, threading, pressing and / or cold upsetting.
  • the metallic molded bodies coated with an oxalate layer according to the invention are preferably dried before being coated with a lubricant composition.
  • a lubricant composition With water-based In lubricant compositions, drying of the oxalate layer is not necessary, even if it is nevertheless dried in some process sequences.
  • the oxalate layer according to the invention predominantly contains or preferably consists essentially of iron (II) oxalate, iron (II) oxalate dihydrate and / or other oxalates. It preferably contains no halogen compounds, no phosphorus compounds and / or no sulfur compounds. It preferably contains only traces or no environmentally unfriendly heavy metals.
  • the iron oxalates are usually crystalline.
  • Figure 1 shows a typical example of a crystalline iron oxalate layer.
  • the oxalate crystals often have an average crystal size in the range from 3 to 12 ⁇ m.
  • the oxalate layer usually looks light gray, greenish yellow and / and greenish gray.
  • the dried conversion layer is closed to at least 90 percent by area or even to at least 95 percent by area and is deposited as firmly as possible on the metallic surface.
  • the closeness can be roughly estimated on the basis of scanning electron microscope images, whereby a higher resolution should be used to identify pores and access routes to the metallic surface.
  • the layer weight of the dried oxalate layer is in the range from 1.5 to 15 g / m 2 , in particular in the range from 3 to 12 g / m 2 , from 4 to 10 g / m 2 or from 5 to 7 g / m 2 .
  • the ratio of pickling removal to layer weight BA: SG of the dried conversion layer is in the range from (0.35 to 0.70): 1, from (0.36 to 0.55): 1 or from (0.37 to 0.45 ) : 1.
  • the layer thickness of the oxalate layer is preferably in the range from 0.1 to 6 ⁇ m and in particular in the range from 0.5 to 4 ⁇ m, from 1 to 3 ⁇ m, from 1.5 up to 2.5 ⁇ m or at about 2 ⁇ m.
  • the preferred oxalate layer thickness can vary somewhat depending on the type of shaped body: In the case of more sophisticated shaped bodies and / or more demanding degrees of deformation, it is preferably somewhat greater, ie for example about 4 ⁇ m instead of about 2 ⁇ m.
  • the lubricant compositions 6.) to 8.) are also suitable for the heaviest cold forming.
  • the lubricant layer is produced with a lubricant composition which contains an organic polymer and / or copolymer.
  • the metallic moldings are thoroughly dried after being coated with the lubricant composition, in particular with warm air and / or radiant heat. This is often necessary because, as a rule, the water content in coatings interferes with cold forming, because otherwise the coating can be formed insufficiently and / and because a coating of poorer quality can be formed. Otherwise vapor bubbles, surface defects or deformation defects can occur. In general, rusting can also occur here, but this can be prevented or reduced with as largely closed oxalate layers as possible and rapid further treatment with a lubricant composition. It is advisable to dry the oxalate layer quickly, e.g. with hot air, if longer idle times are to be expected before coating with a lubricant composition.
  • the lubricant layer produced according to the invention preferably has a layer thickness in the range from 0.01 to 40 ⁇ m after drying, which is preferably made thinner or thicker depending on the type of lubricant composition.
  • their average dry layer thickness is preferably in the range from 0.03 to 30 ⁇ m, from 0.1 to 15 ⁇ m, from 0.5 to 10 ⁇ m, from 1 to 5 ⁇ m or from 1.5 to 4 ⁇ m.
  • the mean dry layer thickness of the lubricant layer increases, depending on which basic composition is selected, the lubricant layers of the lubricant composition 5.) usually being the thinnest.
  • cold forming achieves the best results with lubricant compositions which, like the products from Chemetall GmbH under the brand name Gardomer®, have a content of at least 5% by weight of organic polymers and / or copolymers. They show an optimal compatibility of the layers with the Oxalate layer, also because it does not chemically attack the oxalate layer, and the best forming results in the tests on oxalate layers. This is because they can be used excellently in all types of cold forming together with an oxalate layer according to the invention. In addition, these coatings do not have to be replaced when switching to other types of blanks and / or other types of cold forming.
  • the oxalate layers according to the invention can be kept thinner than the zinc phosphate layers of the prior art, so that, despite the same performance during cold forming, lower chemical consumption occurs significantly reduces operating costs.
  • the oxalate layers according to the invention are phosphate-free.
  • the sludge and waste water of the oxalation process according to the invention are hardly or not contaminated with environmentally unfriendly heavy metals, environmentally unfriendly phosphates and / or environmentally unfriendly additives, so that a simpler and significantly more cost-effective treatment and disposal of the sludge and waste compared to zinc phosphating and also to oxalating according to the prior art Sewage is possible.
  • the oxalated blanks which are also coated with a layer of lubricant, can be produced in particular by pressing, cold forging, Pressing, hitting, upsetting, rolling and / or drawing can be cold-formed.
  • the cold-formed substrates can be used as structural or connecting elements, as sheet metal, wires, wire coils, more complex shaped molded parts, sleeves, profile elements, tubular elements, e.g. as welded seamless tubes, cylinders and / or as components in particular in energy technology, vehicle construction, device construction or mechanical engineering.
  • the oxalation process according to the invention is very superior to the oxalation and zinc phosphating processes of the prior art.
  • the complete or extensive freedom from environmentally unfriendly heavy metals and from phosphorus, halogen and sulfur compounds are particularly advantageous in the process according to the invention.
  • Particularly advantageous in the method according to the invention are the simple bath management and the much simpler control and regulation of the bath and layer quality by checking the temperature, treatment time and acidity using GS points.
  • the method according to the invention is therefore much simpler than zinc phosphating, for example. It is also not necessary to control and adjust the free acid FS, the total acid Fischer GSF and the S value as the ratio of a free acid to the respective total acid. Because when oxalating no free acid FS can be measured because of the complete dissociation of the oxalic acid.
  • Particularly advantageous in the process according to the invention is also the significantly lower amount of sludge compared to phosphating and its complete or extensive freedom from environmentally unfriendly heavy metals and other environmentally unfriendly compounds. Therefore, the disposal effort for sludge and contaminated water is significantly lower and requires significantly less effort and significantly lower costs.
  • test series I the treatment bath was made up with a liquid aqueous concentrate which was prepared by dissolving a given amount of oxalic acid and, if necessary, also by adding accelerator, pigment, surfactant and / or thickener in deionized water.
  • the dilution factor for diluting a concentrate to make a bath ranged from 1 to 3.
  • the treatment bath was made up with a powdery concentrate, which was created by rubbing, mixing in and / or rubbing in powdery oxalic acid and optionally with the addition of nitrate dissolved in water, pigment such as titanium dioxide powder with an average particle size of about 2 microns for increasing the Flowability, surfactant and / or thickener was produced in a compulsory mixer.
  • the powdery concentrate did not have to be dried and was very pourable.
  • the factor for the dissolution of the concentrate in water for the bath preparation was around 1 to 3.
  • test series III a non-free-flowing oxalic acid powder rubbed in a kneader with the titanium dioxide to create a permanently free-flowing product.
  • a paste-like concentrate was produced by mixing oxalic acid together with water, with an accelerator dissolved in water and, if necessary, with pigment such as a suspension, surfactant and / or thickener stabilized with particles with a layered structure in a compulsory mixer.
  • This meterable, highly concentrated, one-component pasty mixture was diluted up to a factor of 20 to form a bath formulation.
  • the coated substrates were rinsed with cold deionized water and then without intermediate drying in the wet-on-wet process (wet-wet process) with an organic copolymer-containing aqueous lubricant composition Gardomer® 6332 from Chemetall GmbH about 2 ⁇ m thick or coated with drawing soap based on stearate such as Lubrifil® VA 1520 from Lubrimetal about 1.5 ⁇ m thick.
  • the cold forming of the sheets coated with the separating layer or the sheets coated with the separating layer and with the lubricant layer and dried was carried out by deep drawing in a laboratory cup pulling device with a universal sheet metal testing machine from Erichsen model 142-20 with a punching force of up to 200 kN in one stage on non-preheated ones Blanks at room temperature.
  • the cold forming of the slugs coated with the separating layer or the slugs coated with the separating layer and the lubricant layer and dried was carried out with a 300 t press from May at 180 t over 300 ms in one stage on non-preheated blanks at room temperature by fully forward backward extrusion.
  • the cold forming of the wire sections and wire coil sections coated with the separating layer or with the separating layer and with the lubricant layer and dried was carried out with a draw bench at up to 3 t at room temperature for more than 300 ms on non-preheated blanks by wire drawing.
  • the wire sections in the inlet were drawn in one step at 1-60 m / s and the wire bundle sections in the inlet were drawn in multiple steps at 0.1-5 m / s.
  • the deformed workpieces were faulty with too thin, insufficiently closed and / or insufficiently adherent oxalate layers and / or too thin lubricant layers, but these are not permissible in industrial production.
  • Cold forming has proven to be very good when the oxalate layer has a layer weight of about 5 to 7 g / m 2 and the lubricant layer based on organic polymer has a layer weight of about 1.5 g / m 2 and when the oxalate layer is largely closed , was evenly and firmly bonded to the substrate.
  • Cold forming has proven to be good when the oxalate layer has a layer weight of about 3 to 4 g / m 2 and the lubricant layer based on organic polymer has a layer weight of about 2.5 g / m 2 lubricant layer and when the oxalate layer is firmly adherent was connected to the substrate.
  • Cold forming has proven to be satisfactory when the oxalate layer has a layer weight of just under 3 g / m 2 and the organic polymer-based lubricant layer has a layer weight of about 2 g / m 2 and when the oxalate layer shows moderate to good adhesive strength. Cold forming has proven to be poor if the oxalate layer was not firmly bonded to the substrate, because then forming was not possible.
  • Examples B46 and B47 in Table 7 are not according to the invention. It has been found that the oxalate layers according to the invention have surface properties which are particularly well suited for application of lubricant and for cold forming.
  • a layer has proven to be a very good oxalate layer that is firmly adhered to the substrate and is sufficiently thick and usually at least 1 ⁇ m thick, if a lubricant layer is then applied before cold forming, or as a rule at least 2 ⁇ m is thick if no lubricant layer is then applied before cold forming.
  • An oxalate layer which has inadequate adhesion and / or an insufficiently closed layer on the substrate has proven to be a less good layer.
  • a thickness of the oxalate layer measured as the layer weight of about 1 g / m 2, is usually sufficient if the oxalate layer is sufficiently closed and rests sufficiently firmly on the metallic substrate. In the case of higher degrees of cold deformation, it is advantageous if the oxalate layer has a layer weight of at least 2 g / m 2 . Therefore, the performance of the oxalate layer during cold forming is more important than the thickness of the oxalate layer. Their performance is only noticeable during the forming process.
  • the tests show very clearly that the quality of the cold forming depends above all on the quality of the oxalate layer and thus on the sufficient cohesion, adhesion and thickness of the oxalate layer.
  • the lubricant layer based on organic polymer and / or copolymer is extremely efficient and robust during cold forming.
  • the lubricant layer based on drawing soap also showed very good performance in cold forming in further tests not shown in detail here.
  • a layer weight of around 1 g / m 2 is usually sufficient for the lubricant layer too.
  • the increased coefficients of friction play a decisive role.
  • cold forming is then quite possible, in particular with low degrees of deformation and / and with sufficiently closed, finely crystalline layers.
  • nitroguanidine acts as an accelerator, but not as a pickling inhibitor.
  • alkali, manganese and zinc phosphating it obviously has an oxidizing effect and accelerates the build-up of the oxalate layer.
  • nitroguanidine does not act as a pickling inhibitor but as an accelerator and that the addition of a pickling inhibitor to the aqueous composition according to the invention is not necessary.
  • the tests showed that with increasing temperature and / or with increasing oxalic acid concentration, the amount of stain removed. It was shown that the pickling removal in a sufficiently accelerated system is usually in a certain ratio to the weight of the layer.
  • the tests showed that a layer formation with the aqueous composition according to the invention is possible in the entire temperature range from 10 to 90 ° C, but that a greater layer thickness is formed at a higher temperature under otherwise the same conditions as the same concentration and the same contact time.
  • the tests showed that the layer weight increases with the temperature of the bath and can also depend on the presence of sufficient accelerator.
  • the tests showed that it should be in the range from 30 to 75%.
  • the adhesive strength of the oxalate layers on the metallic substrate the tests showed that the adhesive strength is positively influenced by a suitable ratio of pickle removal to layer structure and can also be negatively influenced in the case of unsuitable accelerators or their too low or too high concentration.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Lubricants (AREA)
  • Laminated Bodies (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
EP14784475.7A 2013-10-17 2014-10-16 Verfahren zur vorbereitung von metallischen formkörpern für die kaltumformung Active EP3058116B1 (de)

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DE102015211626A1 (de) 2015-06-23 2017-01-19 Richard Bergner Verbindungstechnik Gmbh & Co. Kg Verfahren zur Herstellung eines Verbindungselements sowie Verbindungselement
US10266934B1 (en) * 2016-06-03 2019-04-23 Sabre Communications Corporation Selective coating to inhibit cracking from galvanizing
DE102017121629A1 (de) 2017-09-19 2019-03-21 Schaeffler Technologies AG & Co. KG Verfahren zur Herstellung eines Lagerbauteils sowie Lagerbauteil
BR112021015074A2 (pt) * 2019-02-14 2021-09-28 Chemetall Gmbh Processo para o pré-tratamento de substratos metálicos para conformação a frio, lubrificante reativo acídico, concentrado, substrato metálico pré-tratado, e, uso do substrato metálico
CN110863199A (zh) * 2019-10-30 2020-03-06 湖南金裕环保科技有限公司 不锈钢表面活化剂、制备方法及应用
MX2022010395A (es) * 2020-02-25 2022-09-07 Chemetall Gmbh Metodo de pretratamiento de una etapa de sustratos metalicos para el conformado en frio de metales.
CN112683634B (zh) * 2020-12-04 2022-11-25 成都先进金属材料产业技术研究院股份有限公司 清晰显示冷轧态α+β型钛合金管材金相组织的腐蚀方法
CN114045481B (zh) * 2021-11-24 2023-07-25 永胜机械工业（昆山）有限公司 一种钛复合钢板设备热处理前去除钛表面铁离子的方法

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