EP1350867B1 - A coating solution for metals and metal alloys - Google Patents
A coating solution for metals and metal alloys Download PDFInfo
- Publication number
- EP1350867B1 EP1350867B1 EP03007463A EP03007463A EP1350867B1 EP 1350867 B1 EP1350867 B1 EP 1350867B1 EP 03007463 A EP03007463 A EP 03007463A EP 03007463 A EP03007463 A EP 03007463A EP 1350867 B1 EP1350867 B1 EP 1350867B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- coating solution
- blank
- metal
- solution according
- dithiocarbamate
- 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.)
- Expired - Lifetime
Links
Classifications
-
- 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
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
- C10M111/02—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a non-macromolecular organic compound
-
- 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
- C23C22/07—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 phosphates
- C23C22/23—Condensed phosphates
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/04—Elements
- C10M2201/041—Carbon; Graphite; Carbon black
- C10M2201/0413—Carbon; Graphite; Carbon black used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/06—Metal compounds
- C10M2201/065—Sulfides; Selenides; Tellurides
- C10M2201/066—Molybdenum sulfide
- C10M2201/0663—Molybdenum sulfide used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/085—Phosphorus oxides, acids or salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/085—Phosphorus oxides, acids or salts
- C10M2201/0853—Phosphorus oxides, acids or salts used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/10—Compounds containing silicon
- C10M2201/105—Silica
-
- 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
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/14—Synthetic waxes, e.g. polythene waxes
-
- 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
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/16—Paraffin waxes; Petrolatum, e.g. slack wax
-
- 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
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/18—Natural waxes, e.g. ceresin, ozocerite, bees wax, carnauba; Degras
-
- 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
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
- C10M2207/126—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
-
- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/12—Polysaccharides, e.g. cellulose, biopolymers
-
- 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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
- C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
-
- 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
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
-
- 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
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
-
- 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
- C10N2010/00—Metal present as such or in compounds
- C10N2010/02—Groups 1 or 11
-
- 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
- C10N2010/00—Metal present as such or in compounds
- C10N2010/12—Groups 6 or 16
-
- 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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/243—Cold working
-
- 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
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/015—Dispersions of solid lubricants
- C10N2050/02—Dispersions of solid lubricants dissolved or suspended in a carrier which subsequently evaporates to leave a lubricant coating
Definitions
- the present invention relates to a coating solution to be applied onto the surface of metals or metal alloys, a process for cold forming of metals and metal alloys using said coating solution, and a coated blank made of a metal or a metal alloy.
- a protective film must be formed between the tool and the work piece, which must remain intact during the working process.
- a protective film is mainly made up of molybdenum disulfide dispersions or graphite as lubricants.
- lubricant carriers are applied onto the surface of the workpiece, which can absorb about five times the quantity of lubricants compared to the untreated metal surface.
- the application of such lubricant carriers onto the surface of workpieces is carried out by applying aggressive acids and metallic soaps in huge amounts, which is not desirable from an ecological standpoint.
- US-patent 6,309,477 describes pretreatment chemicals for metal materials to be painted containing at least one kind of sulfur-containing compounds and at least one of phosphorus ion-containing compounds, and an anticorrosive treatment of metal materials.
- JP-A-2001-303262 describes a plated steel sheet covered with an organic film for high corrosion resistance.
- EP-A-0 613 939 describes a graphite-free lubricating oil which comprises a base oil having dispersed therein a carbohydrate and/or a derivative thereof, a film-boosting agent and a dispersant.
- the technical problem underlying the present invention is to provide a new system for cold forming of metals and metal alloys, which should avoid the treatment of the working piece with aggressive acids and/or metallic soaps prior to the cold forming process, but should exhibit at least the same results compared to a cold forming process using workpieces treated with aggressive acids and/or metallic soaps.
- a coating solution to be applied onto the surface of a metal or a metal alloy comprising 2 to 8% (w/v) of a polyphosphate, 2 to 5 % (w/v) of a dithiocarbamate, 5 to 12% (w/v) of graphite and 5 to 12 % (w/v) of molybdenum disulfide.
- the polyphosphate is selected from the group consisting of ammonium polyphosphate and alkali metal polyphosphates, such as sodium polyphosphate, or mixtures thereof.
- the dithiocarbamate is preferably a dialkyl dithiocarbamate, wherein the alkyl groups are the same or different and can have 1 to 12 carbon atoms.
- the dithiocarbamate is a heavy metal dithiocarbamate, wherein the heavy metal is for example molybdenum.
- the dithiocarbamate is a molybdenum dibutyldithiocarbamate.
- the coating solution may further contain at least one component selected from the group consisting of alcohols in an amount of from 0 % to about 100% (v/v); waxes such as polyalkylene waxes, e.g. polyethylene waxes, microcrystalline waxes, and Montan ester waxes, in an amount of from 0 % to about 80 (v/v); emulsifying agents such as alkyloxyethylates and alkylaryloxyethylates, in an amount of from 0 % to about 50% (v/v); pH-modulating agents such as buffers, e.g.
- phosphorous acid and esters thereof in an amount of from 0 % to about 50% (v/v); polymeric compounds such as polyethylene glycols, preferably having a weight average molecular weight of from 500 to 1,000,000, polysaccharides and methylcellulose, in an amount of from 0% to about 50% (v/v); oxides such as silicon dioxide, in an amount of from 0% to about 50% (v/v); friction-reducing agents such as sodium stearate, in an amount of from 0% to about 80% (v/v); defoaming agents such as fatty alcohol polyglycol ethers, in an amount of from 0% to about 50% (v/v); carboxylic acids and derivatives thereof such as 2-phosphonobutanetricarboxylic acid, in an amount of from 0% to about 50% (v/v); organophosphorous compounds such as alkylphosphates, in an amount of from 0% to about 5% (v/v); and phosphates such as boron phosphate, sodium phosphate, P 2 O
- the coating solution has a pH-value ranging from about 3 to about 4, adjusted by the above-defined pH-modulating agent.
- the solvent used for the coating solution of the present invention is H 2 O in an amount of from 0% to 100% (v/v), alcohols, preferably alcohols having up to 10 carbon atoms such as methanol, ethanol, etc., or a mixture of different alcohols, in an amount of from 0% to 100% (v/v), or a H 2 O/alcohol-mixture in an amount of from 0% to 100% (v/v).
- the present invention relates to a process for cold forming of metals or metal alloys, comprising the steps of:
- the blank can be sand-blasted prior to the above process step (a).
- a blank made of a metal or a metal alloy such as steel having a coating obtainable by the above-defined process steps (a) and (b).
- the coating solution of the present invention does not exhibit the severe drawbacks with respect to environmental pollution, and on the other hand the blanks having a coating based on the coating solution of the present invention show at least the same results for the processed workpiece and the tool when compared with blanks having a coating known in the prior art.
- the cold forming process using blanks treated with the coating solution of the present invention is superior from an economical standpoint, i.e. the weight of the coating on the blank is much less as compared to the weight of a coating known in the art.
- 25 cylindrically shaped steel blanks (examples 1 to 25) having a length of 500 mm are immersed in a coating solution containing 2-8 % (w/v) polyphosphate, 2-5 % (w/v) dithiocarbamate, 5-12 % (w/v) graphite and 5-12 % (w/v) molybdenum disulfid for a time period of about 1 min. Then, the blanks having the coating solution on their surfaces are transferred to a drying stove wherein they are dried at a temperature of about 60°C for about 30 min. For comparison, 5 cylindrically shaped steel blanks (Comp. Examples 1 to 5) having a length of 500 mm are coated using the agents and procedure known in the art.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Description
- The present invention relates to a coating solution to be applied onto the surface of metals or metal alloys, a process for cold forming of metals and metal alloys using said coating solution, and a coated blank made of a metal or a metal alloy.
- In cold forming, no heat is applied to the metallic workpiece before forming. However, its temperature can increase during the forming process, as the energy expanded in forming is almost completely converted into heat. The main advantages of cold forming are the saving of materials and working time, the use of lower strength steels, the improved quality of workpieces, lower machine costs, better size accuracy, high surface quality and an extended tool life. In order to achieve these advantages, a protective film must be formed between the tool and the work piece, which must remain intact during the working process. Such a protective film is mainly made up of molybdenum disulfide dispersions or graphite as lubricants. Hitherto, in order to obtain such a protective lubricating film in cold forming processes, lubricant carriers are applied onto the surface of the workpiece, which can absorb about five times the quantity of lubricants compared to the untreated metal surface. However, the application of such lubricant carriers onto the surface of workpieces is carried out by applying aggressive acids and metallic soaps in huge amounts, which is not desirable from an ecological standpoint.
- US-patent 6,309,477 describes pretreatment chemicals for metal materials to be painted containing at least one kind of sulfur-containing compounds and at least one of phosphorus ion-containing compounds, and an anticorrosive treatment of metal materials. JP-A-2001-303262 describes a plated steel sheet covered with an organic film for high corrosion resistance. EP-A-0 613 939 describes a graphite-free lubricating oil which comprises a base oil having dispersed therein a carbohydrate and/or a derivative thereof, a film-boosting agent and a dispersant.
- Therefore, the technical problem underlying the present invention is to provide a new system for cold forming of metals and metal alloys, which should avoid the treatment of the working piece with aggressive acids and/or metallic soaps prior to the cold forming process, but should exhibit at least the same results compared to a cold forming process using workpieces treated with aggressive acids and/or metallic soaps.
- The solution to the above technical problem is achieved by providing the embodiments characterized in the claims.
- In particular, there is provided a coating solution to be applied onto the surface of a metal or a metal alloy, comprising 2 to 8% (w/v) of a polyphosphate, 2 to 5 % (w/v) of a dithiocarbamate, 5 to 12% (w/v) of graphite and 5 to 12 % (w/v) of molybdenum disulfide.
- In a preferred embodiment of the present invention, the polyphosphate is selected from the group consisting of ammonium polyphosphate and alkali metal polyphosphates, such as sodium polyphosphate, or mixtures thereof.
- The dithiocarbamate is preferably a dialkyl dithiocarbamate, wherein the alkyl groups are the same or different and can have 1 to 12 carbon atoms. In a preferred embodiment of the present invention the dithiocarbamate is a heavy metal dithiocarbamate, wherein the heavy metal is for example molybdenum. In a more preferred embodiment of the present invention the dithiocarbamate is a molybdenum dibutyldithiocarbamate.
- In a preferred embodiment of the present invention the coating solution may further contain at least one component selected from the group consisting of alcohols in an amount of from 0 % to about 100% (v/v); waxes such as polyalkylene waxes, e.g. polyethylene waxes, microcrystalline waxes, and Montan ester waxes, in an amount of from 0 % to about 80 (v/v); emulsifying agents such as alkyloxyethylates and alkylaryloxyethylates, in an amount of from 0 % to about 50% (v/v); pH-modulating agents such as buffers, e.g. phosphorous acid and esters thereof, in an amount of from 0 % to about 50% (v/v); polymeric compounds such as polyethylene glycols, preferably having a weight average molecular weight of from 500 to 1,000,000, polysaccharides and methylcellulose, in an amount of from 0% to about 50% (v/v); oxides such as silicon dioxide, in an amount of from 0% to about 50% (v/v); friction-reducing agents such as sodium stearate, in an amount of from 0% to about 80% (v/v); defoaming agents such as fatty alcohol polyglycol ethers, in an amount of from 0% to about 50% (v/v); carboxylic acids and derivatives thereof such as 2-phosphonobutanetricarboxylic acid, in an amount of from 0% to about 50% (v/v); organophosphorous compounds such as alkylphosphates, in an amount of from 0% to about 5% (v/v); and phosphates such as boron phosphate, sodium phosphate, P2O5 etc., in an amount of from 0% to about 80% (v/v); and mixtures thereof containing two or more of said components.
- In a preferred embodiment of the present invention, the coating solution has a pH-value ranging from about 3 to about 4, adjusted by the above-defined pH-modulating agent.
- The solvent used for the coating solution of the present invention is H2O in an amount of from 0% to 100% (v/v), alcohols, preferably alcohols having up to 10 carbon atoms such as methanol, ethanol, etc., or a mixture of different alcohols, in an amount of from 0% to 100% (v/v), or a H2O/alcohol-mixture in an amount of from 0% to 100% (v/v).
- Further, the present invention relates to a process for cold forming of metals or metal alloys, comprising the steps of:
- (a) immersing a blank of a metal or a metal alloy in a bath containing the above-defined coating solution for a time period of from about 30 seconds to about 10 minutes;
- (b) drying said blank having the coating solution on its surface at a temperature ranging from about room temperature to about 80°C, preferably from about 50°C to about 60°C, wherein the drying is carried out preferably in hot air or in a drying stove; and
- (c) subjecting the thus-coated blank to cold forming.
- In the preferred embodiment, the blank can be sand-blasted prior to the above process step (a).
- Further, there is provided a blank made of a metal or a metal alloy such as steel, having a coating obtainable by the above-defined process steps (a) and (b).
- When using the above-defined coating solution for the treatment of blanks ("workpieces") to be processed in cold forming, there can be observed that on the one hand the coating solution of the present invention does not exhibit the severe drawbacks with respect to environmental pollution, and on the other hand the blanks having a coating based on the coating solution of the present invention show at least the same results for the processed workpiece and the tool when compared with blanks having a coating known in the prior art. Moreover, the cold forming process using blanks treated with the coating solution of the present invention is superior from an economical standpoint, i.e. the weight of the coating on the blank is much less as compared to the weight of a coating known in the art. Additionally, in comparison with a coating procedure known in the art, wherein about eleven steps for applying the coating on the blank are necessary, only two steps - (i) immersing the blank in the coating soluting according to the pursuant invention and then (ii) drying the blank - are necessary resulting in a drastically saving of time.
- The present invention will now be further illustrated in the following examples, without being limited thereto.
- 25 cylindrically shaped steel blanks (examples 1 to 25) having a length of 500 mm are immersed in a coating solution containing 2-8 % (w/v) polyphosphate, 2-5 % (w/v) dithiocarbamate, 5-12 % (w/v) graphite and 5-12 % (w/v) molybdenum disulfid for a time period of about 1 min. Then, the blanks having the coating solution on their surfaces are transferred to a drying stove wherein they are dried at a temperature of about 60°C for about 30 min. For comparison, 5 cylindrically shaped steel blanks (Comp. Examples 1 to 5) having a length of 500 mm are coated using the agents and procedure known in the art. The results are summarised in Table 1.
Table 1 Examples blank weight before coating [g] blank weight after coating [g] weight of coating [g] cold forming of coated blanks 1 5583.2 5584.3 1.1 + 2 5558.1 5559.6 1.5 + 3 5560.3 5561.2 0.9 + 4 5562.1 5563.0 0.9 + 5 5552.7 5553.9 1.2 + 6 5532.6 5533.6 1.0 + 7 5538.4 5539.3 0.9 + 8 5552.9 5554.8 1.9 + 9 5564.1 5565.1 1.0 + 10 5554.2 5555.9 1.7 + 11 5553.9 5558.7 2.8 + 12 5547.6 5556.6 1.0 + 13 5560.0 5561.1 1.1 + 14 5568.7 5569.6 0.9 + 15 5573.0 5571.2 0.9 + 16 5563.0 5563.8 0.8 + 17 5572.0 5573.0 1.0 + 18 5570.6 5571.5 0.9 + 19 5562.1 5563.0 0.9 + 20 5559.1 5559.9 0.8 + 21 5570.7 5571.8 1.1 + 22 5572.8 5573.4 0.6 + 23 5561.1 5562.7 1.6 + 24 5563.2 5564.0 0.8 + 25 5563.7 5564.8 1.1 + Comp. Example 1 5531.0 5560.1 29.1 + 2 5526.8 5557.0 30.2 + 3 5535.4 5562.3 26.9 + 4 5533.4 5563.1 29.7 + 5 5532.6 5551.5 18.9 + - As can be taken from Table 1, the coated blanks according to the present invention exhibit a drastically reduced coating weight, but the coating reveals at least the same properties for the blank to be cold formed as the coating of blanks obtained according to the prior art, upon evalution of the processed coated blanks during and after their cold forming (+=good results of the formed blanks after 3 operations in a cold forming process).
Claims (9)
- A coating solution to be applied on the surface of metals or metal alloys, comprising 2 to 8 % (w/v) of a polyphosphate, 2 to 5 % (w/v) of a dithiocarbamate, 5 to 12 % (w/v) of graphite and 5 to 12 % (w/v) of molybdenum disulfide.
- The coating solution according to claim 1, wherein said polyphosphate is selected from the group consisting of ammonium polyphosphate and alkali metal polyphosphates, or a mixture thereof.
- The coating solution according to claim 1 or 2, wherein said dithiocarbamate is a dialkyl dithiocarbamate.
- The coating solution according to claim 3, wherein said dithiocarbamate is a heavy metal dithiocarbamate.
- The coating solution according to any one of claims 1 to 4, further comprising at least one component selected from the group consisting of alcohols, waxes, emulsifying agents, pH-modulating agents, polymeric compounds, oxides, friction-reducing agents, defoaming agents, carboxylic acids and derivatives thereof, organophosphorous compounds, and phosphates, or mixtures thereof containing two or more of said components.
- The coating solution according to any one of claims 1 to 5, having a pH-value ranging from about 3 to about 4.
- A process for cold forming of metals or metal alloys, comprising the steps of:(a) immersing a blank of a metal or a metal alloy in a bath containing the coating solution according to any one of claims 1 to 6, for a time period of from about 30 seconds to about 10 minutes;(b) drying said blank having the coating solution on its surface at a temperature ranging from about room temperature to about 80°C; and(c) subjecting the thus-coated blank to cold forming.
- The process according to claim 7, wherein prior to step (a) the blank is sand-blasted.
- A blank having a coating obtainable by(a) immersing a blank of a metal or a metal alloy in a bath containing the coating solution according to any one of claims 1 to 6, for a time period of from about 30 seconds to about 10 minutes; and(b) drying said blank having the coating solution on its surface at a temperature ranging from about room temperature to about 80°C, resulting in a coated blank.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP03007463A EP1350867B1 (en) | 2002-04-04 | 2003-04-04 | A coating solution for metals and metal alloys |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP02007662 | 2002-04-04 | ||
EP02007662A EP1350866A1 (en) | 2002-04-04 | 2002-04-04 | A coating solution for metals and metal alloys |
EP03007463A EP1350867B1 (en) | 2002-04-04 | 2003-04-04 | A coating solution for metals and metal alloys |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1350867A1 EP1350867A1 (en) | 2003-10-08 |
EP1350867B1 true EP1350867B1 (en) | 2006-07-05 |
Family
ID=28043259
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP03007463A Expired - Lifetime EP1350867B1 (en) | 2002-04-04 | 2003-04-04 | A coating solution for metals and metal alloys |
Country Status (1)
Country | Link |
---|---|
EP (1) | EP1350867B1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2220200B1 (en) | 2007-11-16 | 2018-09-19 | Henkel AG & Co. KGaA | Dry-film, anti-corrosive cold forming lubricant |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2378084A1 (en) * | 1977-01-21 | 1978-08-18 | Rostovsky O Neftemaslozavod | PROCESS FOR PREPARING PLASTIC AND LIQUID LUBRICANTS |
JP2586871B2 (en) * | 1993-03-02 | 1997-03-05 | 協同油脂株式会社 | Non-graphite lubricating oil dispersed in oil |
JPH08157859A (en) * | 1994-12-02 | 1996-06-18 | Showa Shell Sekiyu Kk | Lubricating grease composition |
JP3973323B2 (en) * | 1998-08-13 | 2007-09-12 | 日本ペイント株式会社 | Non-chromium treatment with sulfur-containing and phosphorus-containing compounds |
JP2001303262A (en) * | 2000-04-20 | 2001-10-31 | Nippon Steel Corp | Surface-treated steel sheet with highly corrosion resistant organic coating |
-
2003
- 2003-04-04 EP EP03007463A patent/EP1350867B1/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
EP1350867A1 (en) | 2003-10-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2334716C (en) | Composition and process for lubricated plastic working of metals | |
EP0917559B1 (en) | Waterborne lubricant for the cold plastic working of metals | |
US7414012B2 (en) | Aqueous lubricant for plastic working of metallic material and method for forming lubricant film | |
EP2220200B1 (en) | Dry-film, anti-corrosive cold forming lubricant | |
US20030130137A1 (en) | Aqueous lubricant for plactic working of metallic material and method of lubricant film processing | |
US4758359A (en) | Aqueous metal working lubricant containing a complex phosphate ester | |
US4147639A (en) | Lubricant for forming metals at elevated temperatures | |
EP0177021B1 (en) | Lubricant for plastic working of metals | |
EP0412788B1 (en) | Lubrication method for cold plastic working of metallic materials | |
US5547595A (en) | Aqueous lubricant and process for cold forming metal, particularly pointing thick-walled metal tubes | |
US7105472B2 (en) | Coating solution for metals and metal alloys | |
CN107523404B (en) | Water-based antirust metal cold forging lubricant and preparation method thereof | |
EP1350867B1 (en) | A coating solution for metals and metal alloys | |
CN108138327B (en) | Steel wire rod excellent in corrosion resistance and appearance after working | |
CA1154745A (en) | Metal drawing compound composition and method of use | |
WO1995018202A1 (en) | Lubricant for forming aluminum and aluminum alloy plates, and aluminum and aluminum alloy plates for forming | |
US5091100A (en) | Fatty triglyceride-in-water solid film high temperature prelube emulsion for hot rolled steel | |
EP1350866A1 (en) | A coating solution for metals and metal alloys | |
US3192619A (en) | Lubricant coating composition and method of cold forming metals | |
EP0200167B1 (en) | Process to facilitate cold forming | |
EP1698682A1 (en) | Water-base lubricant for plastic forming | |
WO2017057385A1 (en) | Steel wire with excellent corrosion resistance and appearance after processing | |
CN114854483A (en) | Water-soluble tungsten-molybdenum grinding fluid | |
EP4174155A1 (en) | Boron-free water-based lubricant for plastic working | |
JPH0448839B2 (en) |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL LT LV MK RO |
|
17P | Request for examination filed |
Effective date: 20040212 |
|
AKX | Designation fees paid |
Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR |
|
17Q | First examination report despatched |
Effective date: 20050125 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20060705 Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060705 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060705 Ref country code: BE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060705 Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060705 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060705 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060705 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060705 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REF | Corresponds to: |
Ref document number: 60306569 Country of ref document: DE Date of ref document: 20060817 Kind code of ref document: P |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20061005 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20061005 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20061005 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20061016 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: NV Representative=s name: A. BRAUN, BRAUN, HERITIER, ESCHMANN AG PATENTANWAE |
|
NLV1 | Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20061205 |
|
EN | Fr: translation not filed | ||
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20070410 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070511 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20061006 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070404 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PFA Owner name: ZEPF, WALTER Free format text: ZEPF, WALTER#BYK-GULDEN-STRASSE 10 + 13#78467 KONSTANZ/BODENSEE (DE) -TRANSFER TO- ZEPF, WALTER#BYK-GULDEN-STRASSE 10 + 13#78467 KONSTANZ/BODENSEE (DE) |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060705 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060705 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070430 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060705 Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070404 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070106 Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060705 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20090401 Year of fee payment: 7 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20100404 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100404 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PCAR Free format text: NEW ADDRESS: HOLBEINSTRASSE 36-38, 4051 BASEL (CH) |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20150429 Year of fee payment: 13 Ref country code: CH Payment date: 20150429 Year of fee payment: 13 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 20150429 Year of fee payment: 13 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 60306569 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MM01 Ref document number: 332399 Country of ref document: AT Kind code of ref document: T Effective date: 20160404 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160430 Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20161101 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160430 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160404 |