EP3924454A1 - Procédé simplifié de traitement préalable de substrats métalliques pour la déformation à froid et lubrifiant réactif approprié - Google Patents

Procédé simplifié de traitement préalable de substrats métalliques pour la déformation à froid et lubrifiant réactif approprié

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Publication number
EP3924454A1
EP3924454A1 EP20703464.6A EP20703464A EP3924454A1 EP 3924454 A1 EP3924454 A1 EP 3924454A1 EP 20703464 A EP20703464 A EP 20703464A EP 3924454 A1 EP3924454 A1 EP 3924454A1
Authority
EP
European Patent Office
Prior art keywords
lubricant
wax
waxes
group
reactive lubricant
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP20703464.6A
Other languages
German (de)
English (en)
Inventor
Frank Hollmann
Benjamin Guettler
Yinfeng SHI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chemetall GmbH
Original Assignee
Chemetall GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chemetall GmbH filed Critical Chemetall GmbH
Publication of EP3924454A1 publication Critical patent/EP3924454A1/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/46—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
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
    • C10M2207/123—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms polycarboxylic

Definitions

  • the present invention relates to a simplified method for pretreating metallic substrates for cold forming, to a corresponding reactive lubricant, and to a metallic substrate pretreated with the method and its use.
  • Cold forming takes place at temperatures below the recrystallization temperature of the shaped body to be formed; temperatures of up to about 450 ° C. are usually used.
  • the heating can occur solely through the frictional forces 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. If, however, the shaped bodies to be reshaped are preheated to temperatures, for example, in the range from 650 to 850 ° C., from 850 to 1,250 ° C. or from 650 to 1250 ° C., one speaks of warm forging or forging. In addition, elevated to high pressures usually occur during cold forming, e.g. B. for steel in the range from 200 MPa to 1 GPa and sometimes even up to 2 GPa.
  • the shaped bodies to be reshaped are mostly strips, sheets, slugs, wires, wire coils, more complex shaped molded parts, sleeves, profiles such as hollow or solid profiles, tubes, circular blanks, discs, rods, rods or cylinders.
  • the shaped bodies can in principle consist of any metallic material. Most of the time, the shaped body consists essentially of steel.
  • Cold forming primarily comprises slide drawing (tensile compression forming), ironing pressing, ironing (forming to final dimensions) and / or deep drawing, thread rolling and / or thread hammering, pressing such as e.g. Cold extrusion (pressure forming) and / or cold stamping.
  • non-reactive forming oils are usually used for cold forming of metallic moldings with very low degrees of deformation and correspondingly lower forces
  • at higher degrees of deformation at least one coating is usually used as a separating layer between the mold and the tool in order to avoid cold welding of the mold and the tool.
  • a highly crystalline coating is usually applied in a phosphoric acid solution in the presence of zinc salts, which does not melt at the prevailing temperatures, is chemically and physically (e.g. by chemical sorption) grown with the metallic substrate and prevents cold welding because it acts as a separation between The tool and the substrate are used during the forming process.
  • the lubricant composition used on this separating layer can be of very different nature.
  • the lubricant layer is preferably produced with a lubricant composition which contains soap, oil and / or organic polymer and / or copolymer.
  • the mentioned (water-based) lubricant compositions have an alkaline pH value, while conventional baths for applying the separating layer have an acidic pH value.
  • it is essential to rinse between the two treatments and, if necessary, to remove excess acid with a suitable neutralizing agent. This results in a common process sequence, which can be structured as follows:
  • step 1 all types of residues, which may come from the manufacture of a fresh steel substrate, for example, are removed with strong alkaline cleaners at very high temperatures.
  • Step 2 involves acid pickling the surface including removing scale and rust.
  • the temperature can be between ambient temperature and 60 ° C.
  • This step 3 is preferably carried out using water-based seed crystal solutions at room temperature to 55 ° C.
  • step 4 the conversion treatment is then carried out using an acidic, water-based zinc phosphating solution.
  • step 5 includes a rinsing step followed by an optional neutralization.
  • Step 6 is lubrication. Depending on the lubricant, this can be done in the presence of water-based polymers at 55 to 60 ° C, water-based soaps at 70 to 85 ° C or water-based salt carrier crystals at over 70 ° C.
  • step 3 can be dispensed with. Since the bath composition in step 4 is more simply designed than zinc phosphating, the process has fewer control parameters, which makes it easier to operate.
  • DE 2102295 B2 describes a reactive lubricating oil in which an iron-containing phosphate layer is formed on the surface.
  • this composition contains less than 20 wt .-% water, so it has an oil-containing main phase and can therefore not be described as water-based.
  • VOC volatile organic substances
  • oil-based systems have a problem with regard to occupational safety, since they are flammable and must be stored as hazardous goods at flash points> 150 ° C.
  • Water-based, i.e. Emulsified systems usually have no problems with the fire load due to the water content - more than 35% by weight. The VOC load is also lower, as the maximum temperature of the system is limited by the boiling point of the water.
  • the object of the present invention was therefore on the one hand to provide a water-based pre-treatment method for cold forming in which as few treatment steps as possible are required.
  • step 4 it is possible to combine the steps of conversion treatment (step 4) and lubrication (step 6) in one step and accordingly omit the neutralization in between (step 5):
  • the object of the present invention to provide a pretreatment process for cold forming in which the combined conversion and lubricant layer applied in step 3 has such a high layer weight and such strong adhesion to the metallic substrate that it also is still sufficient before the forming process, ie that it is not removed so far during the forming process that an effective separation of the tool from the workpiece and an effective reduction of the friction coefficient no longer takes place.
  • step 3 In order to ensure that the combined conversion and lubricant layer applied in step 3 is still sufficiently present after the forming process, it has been found necessary in the present case that said combined layer as well as a pure crystalline, for example oxalate-based conversion layer, both chemically - in the form of chemical bonds between crystals and surface - as well as physically, ie by adsorption, is bound to the surface of the metallic substrate, and not only physically as is the case for the non-reactive lubricants available.
  • oxalate-based conversion layer both chemically - in the form of chemical bonds between crystals and surface - as well as physically, ie by adsorption, is bound to the surface of the metallic substrate, and not only physically as is the case for the non-reactive lubricants available.
  • At least one accelerator comprising nitroguanidine and / or at least one iron (III) source
  • the at least one film former is selected from the group consisting of homo- and copolymers of ethylene, propylene, styrene, (meth) acrylic acid, (meth) acrylate, vinylamine, vinylformamide, vinylpyrrolidone, vinylcaprolactam, vinyl acetate, vinylimidazole and / or epoxy and their salts and also polyurethanes, polyamides, polyethyleneimines, polyamines and their salts, the at least one wax being selected from the group consisting of non-ionic waxes and cationically stabilized waxes, and
  • the at least one emulsified lubricating oil is selected from the group consisting of synthetic oils, mineral oils, vegetable oils and animal oils.
  • the water-based combined treatment step in step 3 is therefore advantageously largely VOC-free, ie no VOCs such as volatile oils are added to the reactive lubricant in step 3.
  • the metallic substrate to be reshaped is subjected to the treatment steps listed “one after the other”, then this should not exclude the possibility that one or more further treatment steps such as, for example, may be performed before, between and / or after the treatment steps listed. Further rinsing steps can be carried out. According to a preferred embodiment, however, no further treatment steps are carried out before the cold forming.
  • water-based means that the corresponding composition, in particular the acidic, reactive lubricant, consists of more than 35% by weight of water.
  • a “reactive lubricant” is a lubricant that reacts with the metallic substrate and thus forms a combined conversion and lubricant layer on it.
  • oxalic acid also includes the singly and doubly deprotonated form of oxalic acid.
  • iron (III) source in the context of the present invention is preferably to be understood as a water-soluble iron (III) salt such as iron (III) nitrate.
  • a water-soluble iron (II) salt in combination with an oxidizing agent suitable for generating iron (III) ions is, however, also conceivable as an iron (III) source.
  • a “film former” is a homopolymer or copolymer in which the individual polymer chains are physically cross-linked and which has viscoelastic properties.
  • (meth) acrylic acid stands for methacrylic acid and / or acrylic acid
  • (meth) acrylate correspondingly for methacrylate and / or acrylate.
  • a “wax” is to be understood as meaning a substance that is kneadable at 20 ° C, solid to brittle-hard, has a coarse to fine crystalline structure, has a color ranging from shining to opaque, but not glass-like, over 40 ° C melts without decomposition, is slightly liquid (not very viscous) a little above the melting point, has a strongly temperature-dependent consistency and solubility and can be polished under slight pressure. If more than one of the properties listed above is not met, the substance is therefore not a wax.
  • the wax is preferably emulsified in aqueous solution by nonionic and / or cationic substances.
  • a “non-ionic wax” can in particular also be a wax which is formed by non-ionic groups or by non-ionic substances, such as e.g. Surfactants, more preferably by non-ionic substances, in particular by non-ionic surfactants, is stabilized in the acid, so that the wax is in the form of a wax emulsion.
  • non-ionic wax can in particular also be a wax which is formed by non-ionic groups or by non-ionic substances, such as e.g. Surfactants, more preferably by non-ionic substances, in particular by non-ionic surfactants, is stabilized in the acid, so that the wax is in the form of a wax emulsion.
  • a “cationically stabilized wax” is a wax that is formed by cationic groups or by cationic substances, such as surfactants, more preferably by cationic Substances, in particular by cationic surfactants, is stabilized in the acid, so that the wax is in the form of a wax emulsion.
  • a “combined conversion and lubricant layer” in the context of the present invention means, on the one hand, a layer which is homogeneous in the chemical sense and which combines the properties of a conversion layer and a lubricant layer. On the other hand, however, it can also be a coating that has chemically heterogeneous areas above or next to one another - that is, areas with a conversion layer and areas with a lubricant layer.
  • the metallic substrate to be reshaped can be, for example, a band (known to those skilled in the art as a “coil”), a sheet metal, a wire - possibly pre-drawn - a wire bundle, a complex shaped part, a sleeve, a profile such as a hollow or Solid profile, a tube, a round blank, a disc, a rod, a rod, a cylinder, a slug, a blank or a semi-finished product.
  • a slug to be a disk or a section of a wire, a wire bundle or a rod.
  • the metallic substrate to be cold formed can in principle consist of any metallic material. It preferably consists for the most part, that is to say more than 50 mol%, of a metal or a metal alloy which is selected from the group consisting of iron, steel, aluminum, aluminum alloys, copper, copper alloys, magnesium , Magnesium alloys, titanium and titanium alloys.
  • the metallic substrate to be reshaped is more preferably made of iron materials such as steel, alloyed steels or stainless steels.
  • step 1 of the method according to the invention which is preferably carried out, the metallic substrate is first cleaned mechanically or chemically.
  • the chemical cleaning is preferably done by immersion in a water-based, alkaline cleaning bath for 10 to 30 minutes at 70 to 90 ° C., the mechanical cleaning preferably by means of dry or wet descaling or blasting.
  • the metallic substrate is then rinsed.
  • the rinsing is preferably done with deionized water or city water.
  • step 2 which is also preferably carried out, the metallic substrate is then pickled.
  • the pickling is preferably done by immersion in a water-based, acidic pickling bath for several seconds to 30 minutes at up to approx. 70 ° C.
  • the pickling is mostly carried out in - if necessary, inhibited - hydrochloric acid, sulfuric acid or phosphoric acid. It can be done in one bath, but also in a cascade of baths.
  • the metallic substrate is then rinsed. The rinsing is preferably done with deionized water or city water.
  • the reactive lubricant in step 3 of the process according to the invention preferably contains between 2 and 500 g / l, particularly preferably between 5 and 100 and very particularly preferably between 10 and 50 g / l of oxalic acid, each calculated as oxalic acid Dihydrate.
  • the oxalic acid is preferably added to the reactive lubricant as oxalic acid dihydrate, which is cheaper and less hygroscopic.
  • the reactive lubricant in step 3 contains, as component b), at least one accelerator which comprises nitroguanidine and / or at least one iron (III) source.
  • the nitroguanidine content is preferably in the range from 0.01 to 20 g / l, particularly preferably from 0.5 to 10 g / l and very particularly preferably from 1.0 to 5 g / l, while the iron content ( III) preferably in the range from 0.0004 to 2 g / l, particularly preferably from 0.04 to 2 g / l and very particularly preferably from 0.4 to 2 g / l, calculated as iron (III) nitrate, lies.
  • the reactive lubricant therefore contains, in addition to component c)
  • the reactive lubricant preferably contains as component b) at least one accelerator which comprises at least one iron (III) source.
  • an iron (III) source has the advantage that finer layers, i.e. those with smaller crystals (diameter: approx. 3-5 ⁇ m) are formed, the layer formation being faster, so that shorter gas times are required (less gas development, less material and chemical loss).
  • a particularly suitable iron (III) source is iron (III) nitrate because of its particularly good solubility, its easy availability and its good accelerating effect.
  • component c) of the reactive lubricant in step 3 comprises at least one film former selected from the group consisting of homo- and copolymers of ethylene, propylene, styrene, (meth) acrylic acid, (meth) acrylate, vinylamine, vinylformamide, Vinylpyrrolidone, vinylcaprolactam, vinyl acetate, vinylimidazole and / or epoxide and their salts and also Po lyurethanes, polyamides, polyethyleneimines, polyamines and their salts, the total content of these film formers in the reactive lubricant is preferably in the range from 0.01 to 100 g / l, especially preferably from 0.5 to 30 g / l and very particularly preferably from 1 to 20 g / l.
  • component c) comprises at least one wax selected from the group consisting of non-ionic waxes and cationically stabilized waxes
  • the total content of these waxes in the reactive lubricant is preferably in the range from 0.1 to 300 g / l, especially or preferably from 0.1 to 150 g / l and very particularly preferably from 5 to 70 g / l.
  • component c) comprises at least one emulsified lubricating oil
  • the total content of emulsified lubricating oil is preferably in the range from 1 to 50% by weight, particularly preferably from 10 to 40% by weight and very particularly preferably from 20 to 30% by weight. %, calculated as pure oil and based on the total reactive lubricant.
  • component c) of the reactive lubricant in step 3 comprises at least one film former selected from the group consisting of homo- and copolymers of ethylene, propylene, styrene, (meth) acrylic acid, (meth) ac- rylate, vinylamine, vinylformamide, vinylpyrrolidone, vinylcaprolactam, vinyl acetate, vinylimidazole and / or epoxy and their salts, as well as polyurethanes, polyamides, polyethyleneimines, poly amines and their salts.
  • the presence of a film former as described above has the advantage that the resulting lubricating film is anchored on the substrate and thus has a higher hardness and stability. In addition, the result is a more homogeneous layer image.
  • component c) comprises only at least one film former selected from the group consisting of homo- and copolymers of ethylene, propylene, (meth) acrylic acid, (meth) acrylate, vinylamine, vinylformamide, vinylpyrrolidone, vinylcaprolactam , Vinyl acetate, vinylimidazole and / or epoxy and their salts and also polyethyleneimines, polyamines and their salts, in particular consisting of homo- and copolymers of vinylpyrrolidone, but no other film-forming agents.
  • film former selected from the group consisting of homo- and copolymers of ethylene, propylene, (meth) acrylic acid, (meth) acrylate, vinylamine, vinylformamide, vinylpyrrolidone, vinylcaprolactam , Vinyl acetate, vinylimidazole and / or epoxy and their salts and also polyethyleneimines, polyamines and their salts, in particular consisting of homo- and copolymers of vinylpyrrolidone, but no other film-forming agents
  • the above-mentioned film formers especially the homopolymers and copolymers of vinylpyrrolidone, have the advantage of being particularly acid-stable, which means that the water-based, acidic, reactive lubricant in step 3 at the temperatures usually occurring in cold forming processes - also at a very low pH in the range from 0.15 to 1.5 and a high salt content - tends to phase separation and protonation and destabilization to a particularly low degree if only at least one of these film-forming agents is present.
  • the weight-average molar mass of the at least one film former is more preferably in the range from 1,000 to 700,000 g / mol, particularly preferably from 3,000 to 300,000 g / mol and very particularly preferably from 4,000 to 47,500 g / mol.
  • component c) comprises at least one film former selected from the group consisting of polyethylene-polypropylene copolymers, polyethylene and polypropylene homopolymers, in particular polyethylene homopolymers, and vinylamine-vinylformamide Copolymers.
  • Vinylamine-vinylformamide copolymers available for example as Lupamin® 9030 (BASF, Germany), are very particularly suitable.
  • component c) of the reactive lubricant in step 3 comprises at least one wax selected from the group consisting of the non-ionic waxes and the cationically stabilized waxes.
  • a wax as described above has the advantage that it only forms a lubricating film in the molten state, ie during the deformation.
  • Nonionic waxes are preferred, which are each stabilized by at least one nonionic surfactant in the acid, while cationically stabilized waxes are preferred, each by at least one cationic T enside are stabilized in acid.
  • the reactive lubricant in step 3 therefore preferably contains at least one non-ionic or cationic surfactant. This also applies to the following particularly preferred embodiments.
  • component c) comprises only at least one wax selected from the group consisting of nonionic waxes and cationically stabilized waxes, in particular consisting of cationically stabilized waxes, but no other wax.
  • the above-mentioned waxes, in particular the cationically stabilized waxes have the advantage of being particularly acid-stable, which means that the water-based, acidic, reactive lubricant in step 3 at the temperatures that usually occur in cold forming processes - even at very low temperatures low pH in the range from 0.15 to 1.5 and high salt content - tends to phase separation and protonation and destabilization to a particularly low degree if only at least one of these waxes is present.
  • Aqueous dispersions of polypropylene waxes e.g. Aquacer 1041, BYK, Germany
  • Wükonil 0-33A Südered Emulsions-Chemie GmbH, Germany
  • montan waxes e.g. Licowax KST, Clariant, Germany
  • component c) comprises at least one non-ionic wax, which is preferably selected from the group consisting of non-ionic beeswax, non-ionic polyethylene wax, non-ionic HDPE wax and montan wax and is particularly preferably selected is from the group consisting of non-ionic beeswax (eg Aquacer 561, BYK, Germany), non-ionic polyethylene waxes and non-ionic HDPE waxes (eg Aquacer 517, BYK, Germany).
  • “HDPE” stands for high Density polyethylene which, due to weakly branched polymer chains, has a high density, preferably between 0.94 and 0.97 g / cm 3 .
  • the at least one wax preferably comprises at least three, more preferably at least five waxes with different melting points. Due to the resulting coverage of a larger melting point range of preferably at least 50 ° C, more preferably at least 65 ° C, the waxes melt and lubricate at different forming temperatures, thereby optimizing the lubricating performance for different forming requirements. In general, a high load leads to a higher temperature during the forming process, while a low load leads to a lower temperature. In addition, locally different loads and thus with temperatures can occur on a part to be formed.
  • component c) of the reactive lubricant in step 3 comprises at least one film former selected from the group consisting of homo- and copolymers of ethylene, propylene, styrene, (meth) acrylic acid, (meth) ac- rylate, vinylamine, vinylformamide, vinylpyrrolidone, vinylcaprolactam, vinyl acetate, vinylimidazole and / or epoxy and their salts, as well as polyurethanes, polyamides, polyethyleneimines, polyamines and their salts, and at least one wax selected from the group consisting of the nonionic Waxes and the cationically stabilized waxes.
  • film former selected from the group consisting of homo- and copolymers of ethylene, propylene, styrene, (meth) acrylic acid, (meth) ac- rylate, vinylamine, vinylformamide, vinylpyrrolidone, vinylcaprolactam, vinyl acetate, vinylimidazole and / or epoxy and their
  • Nonionic waxes are preferred, which are each stabilized by at least one nonionic surfactant in the acidic environment, while cationically stabilized waxes are preferred are each stabilized by at least one cationic surfactant in the acidic.
  • the reactive lubricant in step 3 therefore preferably contains at least one non-ionic or cationic surfactant. This also applies to the following particularly preferred embodiments.
  • component c) comprises only at least one film former selected from the group consisting of homo- and copolymers of ethylene, propylene, (meth) acrylic acid, (meth) acrylate, vinylamine, vinylformamide, vinylpyrrolidone, vinylcaprolactam , Vinyl acetate, vinylimidazole and / or epoxy and their salts and polyethyleneimines, polyamines and their salts, in particular consisting of homo- and copolymers of vinylpyrrolidone, and only at least one wax selected from the group consisting of nonionic waxes and cationic stabilized waxes, in particular consisting of cationically stabilized waxes, but no other film former and no other wax.
  • film former selected from the group consisting of homo- and copolymers of ethylene, propylene, (meth) acrylic acid, (meth) acrylate, vinylamine, vinylformamide, vinylpyrrolidone, vinylcaprolactam , Vinyl acetate, vinylimidazole and / or epoxy and
  • the above-mentioned film formers and waxes have the advantage of being particularly acid-stable, which means that the water-based, acidic, reactive lubricant in step 3 at the temperatures usually occurring in cold forming processes - even at a very low pH in the range of 0.15 to 1.5 and a high salt content - tends to phase separation and protonation and destabilization to a particularly low degree if only these film formers and waxes are present.
  • the above-described combination of at least three, preferably at least five waxes with different melting points has also proven to be advantageous here.
  • component c) comprises at least one film former selected from the group consisting of polyethylene-polypropylene copolymers, polyethylene and polypropylene homopolymers, in particular polyethylene homopolymers, and vinylamine-vinylformamide Copolymers, preferably from the group consisting of vinylamine-vinylformamide copolymers, and at least one wax selected from the group consisting of non-ionic beeswax, non-ionic polyethylene wax and non-ionic HDPE wax.
  • film former selected from the group consisting of polyethylene-polypropylene copolymers, polyethylene and polypropylene homopolymers, in particular polyethylene homopolymers, and vinylamine-vinylformamide Copolymers, preferably from the group consisting of vinylamine-vinylformamide copolymers, and at least one wax selected from the group consisting of non-ionic beeswax, non-ionic polyethylene wax and non-ionic HDPE wax.
  • component c) of the reactive lubricant in step 3 comprises at least one emulsified lubricating oil.
  • the at least one emulsified lubricating oil is preferably selected from the group consisting of synthetic oils, mineral oils and vegetable oils, more preferably from synthetic oils and mineral oils.
  • a suitable mineral oil is, for example, Shell Gravex 913 (Shell, Netherlands).
  • the at least one emulsified lubricating oil preferably has a viscosity between 20 and 1,000 mPas, in particular between 50 and 800 mPas and particularly preferably between 100 and 600 mPas.
  • naphthenic-aliphatic base oils have viscosities in the aforementioned ranges.
  • Particularly suitable emulsifiers for emulsifying the at least one lubricating oil are nonionic surfactants, more preferably fatty alcohol alkoxylates and very particularly preferably fatty alcohol ethoxylates such as ZOSOLAT 1008/85 (Chemetall, Germany).
  • the total content of emulsifier is preferably in the range from 0.01 to 10% by weight, particularly preferably from 0.1 to 8% by weight and very particularly preferably from 1 to 5% by weight.
  • the reactive lubricant in step 3 of the process according to the invention can, in addition to components a), b) and c), at least one thickener d), at least one defoamer e), at least one pigment f), at least one acid-stable surfactant g) and / or contain at least one corrosion inhibitor h), which is advantageous in certain applications.
  • Particularly advantageous thickeners d) are those based on polysaccharide, polysiloxane, polyvinylamide, i.e. Polyacrylamide or polyethylene glycol.
  • the total content of thickeners d) is preferably in the range up to 100 g / l, more preferably up to 10 g / l.
  • defoamers e) are polymer-based, silicone-free defoamers such as BYK-1711 (BYK, Germany) or defoamers based on 3D silicone such as Foam Ban MS-550 (Münzing, Germany).
  • the total content of defoamers e) is preferably in the range up to 25 g / l, more preferably up to 10 g / l.
  • the pickling attack on the metallic substrate gives rise to gases which - in particular in the presence of at least one acid-stable surfactant g) - can lead to a stable foam settling on the substrate, which, however, can be reduced or even prevented by using a defoamer.
  • pigments f) are hexagonal boron nitride, graphite and molybdenum sulfide. These facilitate the cold forming process particularly effectively.
  • the total content of pigments f) is preferably in the range up to 500 g / l, more preferably up to 50 g / l.
  • Particularly advantageous acid-stable surfactants g) are fatty alcohol alkoxylates and very particularly preferably fatty alcohol ethoxylates such as ZOSOLAT 1008/85 (Chemetall, Germany).
  • the total content of acid-stable surfactants g) is preferably in the range from 0.01 to 10% by weight, particularly preferably from 0.1 to 8% by weight and very particularly preferably from 1 to 5% by weight.
  • the presence of an emulsified lubricating oil in combination with a corrosion inhibitor has the advantage that the corrosion resistance of the metallic substrate is significantly increased, as a result of which the corresponding formed part can be stored longer.
  • corrosion inhibitors h) are nonylphenoxyacetic acid (Irgacor® NPA, BASF, Germany), succinic acid half-esters (Irgacor® L 12, BASF, Germany) and imidazoline derivatives (Amine O, BASF, Germany).
  • the total content of corrosion inhibitors h) is preferably in the range up to 10% by weight, more preferably in the range from 0.1 to 5% by weight, particularly preferably from 0.1 to 3% by weight.
  • the pH of the reactive lubricant in step 3 is preferably below 2.0, more preferably in the range from 0.15 to 1.5. This has the advantage that the pickling attack and thus the Layer formation is intensified.
  • the temperature of the reactive lubricant is preferably in the range from 60 to 95.degree. C., particularly preferably from 75 to 90.degree. C. and very particularly preferably from 80 to 85.degree.
  • the reactive lubricant used in step 3 has proven to be particularly heat-stable. This means that the lubricant remains homogeneous even after several hours or even days at a temperature of 85 ° C, i.e. there is no agglomeration and precipitation of the c) at least one film former, at least one wax and / or at least one emulsified lubricating oil.
  • the metallic substrate is brought into contact with the reactive lubricant, preferably by dipping the substrate into the lubricant or by pouring the lubricant over the substrate.
  • the contact, i.e. Treatment time is preferably in the range from 1 to 40 minutes, particularly preferably from 5 to 30 minutes and very particularly preferably from 8 to 20 minutes.
  • Any sludge that may accumulate in the immersion bath can be removed, as in a phosphating bath, by simple filtration with recovery of the bath.
  • the reactive lubricant is therefore preferably essentially phosphate free, i. no phosphate is added to it.
  • the metallic substrate should not be rinsed, since otherwise there is a risk of the at least one film former, the at least one wax and / or the at least one emulsified lubricating oil which was applied in step 3 to wash off again.
  • the metallic substrate can also be dried in an optional step 4 before it is subjected to a cold forming process.
  • drying may be necessary for water-based lubricants in order to avoid water-based residues if the treated formed bodies, such as wire coils, are tightly packed.
  • the specialist speaks here of a "forced drying”.
  • step 4 drying is preferably carried out by means of hot air at 100 to 280 ° C, which leads to faster and more uniform drying of the lubricant layer and minimizes water residues.
  • the drying with the aid of an aid such as hot air or an oven does not mean drying of the metallic substrate in the air - possibly still hot / warm from step 3.
  • the method according to the invention is basically suitable for all possible cold forming processes, in particular for
  • slide drawing tensile compression forming
  • welded or seamless pipes hollow profiles, solid profiles, wires or rods such as in wire drawing or pipe drawing
  • a pressing such as e.g. Cold extrusion (pressure forming) e.g. of hollow bodies, solid bodies,
  • a cold heading e.g. from wire sections to connecting elements such as Nut or screw blanks.
  • the metallic substrates treated with the process according to the invention can be cleaned well, i. E.
  • the combined conversion and lubricant layers can be removed using alkaline cleaners, acids or stains - as they are also used in the case of phosphating with an overlying polymer lubricant.
  • the present invention also relates to a water-based, acidic, reactive lubricant for the cold forming of metallic substrates, the
  • At least one accelerator comprising nitroguanidine and / or at least one iron (III) source
  • the at least one film former is selected from the group consisting of homo- and copolymers of ethylene, propylene, styrene, (meth) acrylic acid, (meth) acrylate, vinylamine, vinylformamide, vinylpyrrolidone, vinylcaprolactam, vinyl acetate, vinylimidazole and / or epoxy and their salts and also polyurethanes, polyamides, polyethyleneimines, polyamines and their salts, the at least one wax being selected from the group consisting of non-ionic waxes and cationically stabilized waxes, and
  • the at least one emulsified lubricating oil is selected from the group consisting of synthetic oils, mineral oils, vegetable oils and animal oils.
  • the present invention also relates to a concentrate from which the reactive lubricant according to the invention can be obtained by diluting, in particular with water, and optionally adjusting the pH with a pH-modifying substance.
  • the present invention also relates to a pretreated metallic substrate which can be obtained with the above-described method according to the invention.
  • the metallic substrate thus obtainable has a combined conversion and lubricant layer, the layer weight of which, determined by the gravimetric detachment method, is calculated in the range from 0.3 to 15 g / m 2 , preferably from 0.3 to 10 g / m 2 as a lubricant layer, and in the range from 0.3 to 30 g / m 2 , preferably from 1.5 to 15 g / m 2 , calculated as the separation / conversion layer.
  • the combined layer can be set separately and individually.
  • a longer treatment time in step 3 of the method according to the invention results in a thicker separating / conversion layer, i.e. a higher layer weight calculated as a separating / conversion layer, while a higher concentration of film former / wax / emulsified lubricating oil, i.e. component c) of the reactive lubricant according to the invention, results in a thicker lubricant layer, i.e. a higher layer weight calculated than the lubricant layer.
  • a combined conversion and lubricant layer tailored to the respective cold forming conditions can be produced.
  • the combined conversion and lubricant layers “survive” conventional cold forming processes At least 10%, preferably at least 15%, particularly preferably at least 20% and very particularly preferably at least 23% of the total layer weight (calculated as the lubricant layer and calculated as the separating / conversion layer) still remains on a pretreated and drawn high-carbon wire if this one forming simulation on the drawbench in one operation which comprises a total reduction in diameter of at least 40%, preferably of at least 50% and particularly preferably of at least 55% in four steps.
  • the total reduction in% is calculated as [(initial diameter: final diameter) - 1] x 100. This enables the formed substrate to be protected against corrosion temporarily.
  • the subject matter of the present invention is the use of a pretreated metallic substrate obtainable with the method according to the invention in a cold forming process, for example for the production of pipes, wires, connecting elements, profiles, sealing or gear parts.
  • the acidic, reactive lubricants A to I were used which, in addition to water, also contained the constituents listed in Table 1.
  • the reactive lubricants A to E were each heated to different temperatures with stirring and kept at the corresponding temperature for several hours. Up to a temperature of 85 ° C the lubricants remained homogeneous, i.e. there was no agglomeration and precipitation of the waxes and film formers contained. This was not the case with lubricant D even after 14 hours and with lubricant E even after more than 5 days. However, the lubricant F has proven to be extremely temperature-stable. Even at a temperature of 95 ° C., no agglomeration and precipitation occurred after more than 5 days.
  • the gravimetric detachment method is carried out as follows:
  • the separating / conversion layer is dissolved in 10-20% sodium hydroxide solution with triethylamine / EDTA.
  • the metallic substrate is weighed again.
  • the weight difference between 1) and 3) based on the surface results in the layer weight calculated as the lubricant layer, while the weight difference between 3) and 5) based on the surface is the layer weight calculated as the separation / conversion layer.
  • a high-carbon wire of quality ST1375 / 1570 (Voestalpine, Austria) was pretreated with the reactive lubricant E as described above. The diameter of the wire was then reduced in four steps from 10.9 mm to 7.0 mm on a draw bench (see Table 4). Three different pulling speeds were used: 20 m / s, 40 m / s and 60 m / s. The forming was successful at all pulling speeds. There were no defects such as scratches on the drawn wire. The tensile force measured was comparable to that of conventional polymer lubricants. The surface temperatures that occurred were below 110 ° C. Table 4:
  • the total layer weight was therefore approx. 15 g / m 2 , of which approx. 3.5 g / m 2 were left after the deformation. This means that about 25% of the layer was retained.
  • a high carbon wire of the quality ST1375 / 1570 (Voestalpine, Austria) was pretreated with the reactive lubricant F as described above.
  • the diameter of the wire was then reduced on a drawbench in four steps from 11 to 6.7 mm (Exp. I and Exp. II) and in two steps from 11 to 7.4 mm (Exp. III) (see Tab . 6).
  • Three different pulling speeds were used, namely 30 m / s (Exp. I), 60 m / s (Exp. II) and 40 m / s (Exp. III), whereby the diameter of the wire per forming step is 20% ( Exp. I and Exp. II) or 35%.
  • the forming was successful in all cases. There were no errors such as Scratches on the drawn wire.
  • the tensile force measured was comparable to conventional polymer lubricants.
  • the surface temperatures that occurred were below 110 ° C.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Lubricants (AREA)

Abstract

La présente invention concerne un procédé simplifié de traitement préalable de substrats métalliques pour la déformation à froid, selon lequel un substrat métallique est successivement nettoyé, puis rincé, 2) de préférence décapé, puis rincé, 3) mis en contact avec un lubrifiant réactif acide à base d'eau, lequel contient a) de l'acide oxalique, b) au moins un accélérateur qui comprend de la nitroguanidine et/ou au moins une source ferrique, et c) au moins un agent filmogène, au moins une cire et/ou au moins une huile lubrifiante émulsifiée, et est éventuellement séché, ledit au moins agent filmogène étant sélectionné dans le groupe comprenant des homopolymères et des copolymères d'éthylène, de propylène, de styrol, d'acide (meth)acrylique, de (meth)acrylate, de vinylamine, de vinylformamide, de vinylpyrrolidone, de vinylcaprolactame, de vinylacétate, de vinylimidazole et/ou d'époxyde et leurs sels ainsi que polyuréthanes, polyamides, polyéthylénimines, polyamines et leurs sels, ladite au moins une cire étant sélectionnée dans le groupe comprenant des cires non ioniques et des cires stabilisées par voie cationique, et ladite au moins une huile lubrifiante émulsifiée étant sélectionnée dans le groupe comprenant huiles synthétiques, huiles minérales, hiles végétales et huiles animales, l'invention concernant également un lubrifiant réactif correspondant ainsi qu'un substrat métallique prétraité selon le procédé et son utilisation.
EP20703464.6A 2019-02-14 2020-02-07 Procédé simplifié de traitement préalable de substrats métalliques pour la déformation à froid et lubrifiant réactif approprié Pending EP3924454A1 (fr)

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PCT/EP2020/053089 WO2020165035A1 (fr) 2019-02-14 2020-02-07 Procédé simplifié de traitement préalable de substrats métalliques pour la déformation à froid et lubrifiant réactif approprié

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CN (1) CN113454196A (fr)
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CA (1) CA3128951A1 (fr)
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US20240166968A1 (en) 2021-04-01 2024-05-23 Chemetall Gmbh One-step pretreatment method of metallic substrates at non-neutral ph values for metal cold forming

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GB823373A (en) * 1955-05-24 1959-11-11 Pyrene Co Ltd Improvements relating to the formation of coatings on metal surfaces
NL125777C (fr) * 1961-03-07
DE2102295C3 (de) 1971-01-19 1981-01-29 Metallgesellschaft Ag, 6000 Frankfurt Schmiermittel für die spanlose Kaltverformung
DE2125503A1 (de) * 1971-05-22 1972-12-14 Metallgesellschaft Ag Oxalierungsverfahren für Eisen- und Stahloberflächen
JPS6019357B2 (ja) * 1977-06-16 1985-05-15 日本パ−カライジング株式会社 金属の冷間加工用潤滑剤
JPS5672090A (en) * 1979-11-19 1981-06-16 Nippon Parkerizing Co Ltd Surface treatment of metal
JPS62170484A (ja) * 1986-01-21 1987-07-27 Nippon Parkerizing Co Ltd ステンレス鋼の冷間加工用潤滑処理方法
JPS62174386A (ja) * 1986-01-27 1987-07-31 Nippon Parkerizing Co Ltd しゆう酸塩皮膜化成処理液および該処理液によるステンレス鋼材の化成処理方法
JP3193798B2 (ja) * 1993-01-13 2001-07-30 日本パーカライジング株式会社 金属冷間加工用の複合皮膜形成用金属表面処理液及び複合皮膜形成方法
DE10308237B4 (de) * 2003-02-25 2014-01-16 Chemetall Gmbh Verfahren zur Beschichtung von metallischen Oberflächen, zugehörige Zusammensetzung und ihre Verwendung
DE102007011553A1 (de) * 2007-03-09 2008-09-11 Chemetall Gmbh Verfahren zur Beschichtung von metallischen Oberflächen mit einer wässerigen, Polymere enthaltenden Zusammensetzung, die wässerige Zusammensetzung und Verwendung der beschichteten Substrate
KR101278311B1 (ko) * 2008-12-16 2013-07-05 니혼 파커라이징 가부시키가이샤 금속재료용 표면처리제
WO2012032102A1 (fr) * 2010-09-10 2012-03-15 Chemetall Gmbh Procédé de revêtement de surfaces métalliques par un agent de revêtement contenant un polymère, agent de revêtement correspondant et son utilisation
WO2015055756A1 (fr) 2013-10-17 2015-04-23 Chemetall Gmbh Procédé de préparation d'articles façonnés métalliques en vue du formage à froid
JP6545520B2 (ja) * 2015-04-27 2019-07-17 日本パーカライジング株式会社 金属材料用水系潤滑皮膜剤、表面処理金属材料及び金属材料の潤滑皮膜形成方法

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MX2021009484A (es) 2021-09-08
US20220119730A1 (en) 2022-04-21
CN113454196A (zh) 2021-09-28
BR112021015074A2 (pt) 2021-09-28
CA3128951A1 (fr) 2020-08-20

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