EP2450470A1 - Hydroxysulfat-Oberflächenbehandlung - Google Patents
Hydroxysulfat-Oberflächenbehandlung Download PDFInfo
- Publication number
- EP2450470A1 EP2450470A1 EP12000368A EP12000368A EP2450470A1 EP 2450470 A1 EP2450470 A1 EP 2450470A1 EP 12000368 A EP12000368 A EP 12000368A EP 12000368 A EP12000368 A EP 12000368A EP 2450470 A1 EP2450470 A1 EP 2450470A1
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- EP
- European Patent Office
- Prior art keywords
- zinc
- sheet
- treatment solution
- use according
- ions
- 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.)
- Ceased
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- 238000004381 surface treatment Methods 0.000 title 1
- 239000011701 zinc Substances 0.000 claims abstract description 47
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 38
- 239000011248 coating agent Substances 0.000 claims abstract description 31
- 238000000576 coating method Methods 0.000 claims abstract description 31
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 28
- 239000010959 steel Substances 0.000 claims abstract description 28
- 230000007797 corrosion Effects 0.000 claims abstract description 17
- 238000005260 corrosion Methods 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 16
- 230000015556 catabolic process Effects 0.000 claims abstract description 13
- 238000006731 degradation reaction Methods 0.000 claims abstract description 13
- 238000007493 shaping process Methods 0.000 claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- 229910021653 sulphate ion Inorganic materials 0.000 claims abstract description 7
- -1 sulphate ions Chemical class 0.000 claims abstract description 7
- 239000002923 metal particle Substances 0.000 claims abstract description 3
- 239000003921 oil Substances 0.000 claims description 40
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 19
- VCPQWWKLNIMKND-UHFFFAOYSA-L zinc hydroxy sulfate Chemical compound [Zn++].OOS([O-])(=O)=O.OOS([O-])(=O)=O VCPQWWKLNIMKND-UHFFFAOYSA-L 0.000 claims description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 239000011593 sulfur Substances 0.000 claims description 15
- 229910052717 sulfur Inorganic materials 0.000 claims description 15
- 229910045601 alloy Inorganic materials 0.000 claims description 14
- 239000000956 alloy Substances 0.000 claims description 14
- 239000010687 lubricating oil Substances 0.000 claims description 14
- 235000009529 zinc sulphate Nutrition 0.000 claims description 12
- 239000011686 zinc sulphate Substances 0.000 claims description 12
- 150000002500 ions Chemical class 0.000 claims description 8
- 229960001763 zinc sulfate Drugs 0.000 claims description 6
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 230000010287 polarization Effects 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 230000001050 lubricating effect Effects 0.000 claims description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims 1
- 229910001297 Zn alloy Inorganic materials 0.000 abstract description 2
- 238000005461 lubrication Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 13
- 241000282485 Vulpes vulpes Species 0.000 description 7
- 238000000151 deposition Methods 0.000 description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910001335 Galvanized steel Inorganic materials 0.000 description 5
- 239000008397 galvanized steel Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000001464 adherent effect Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000006735 deficit Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 1
- 229910000655 Killed steel Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical class [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/68—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 solutions with pH between 6 and 8
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D22/00—Shaping without cutting, by stamping, spinning, or deep-drawing
- B21D22/20—Deep-drawing
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/53—Treatment of zinc or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/06—Electrolytic coating other than with metals with inorganic materials by anodic processes
Definitions
- the present invention relates to the use of a treatment solution for treating the surface of a steel sheet coated with a metal coating based on zinc or its alloys. It also relates to a method of lubricating such a coated sheet.
- the very high friction exerted by the forming tools on the surface of the sheet causes, on the surface of the sheet, powder or particles based on zinc or its alloys generated by the degradation of the coating.
- the accumulation and / or agglomeration of these particles or powder in the forming tools can cause damage to the formed parts, by formation of pins and / or strictions.
- the sheet may break in the event of insufficient sliding of the sheet into the surface. grip of the formatting tool. These breaks can occur, even by applying a film of oil with a sufficient grammage to the surface of the sheet, ie greater than 1 g / m 2 , because it is not possible to keep a distribution on the surface of the sheet. homogeneous oil film. This is due to the dewetting phenomenon which corresponds to the presence of areas with an oil deficit.
- the oil deficits in certain areas of the oil film due to the dewetting phenomenon are also responsible for a less temporary protection against corrosion of the steel sheet during storage.
- the present invention therefore aims to provide a treatment solution which, applied to the surface of a steel sheet coated with a metal layer based on zinc or its alloys, reduces the degradation of the galvanized surface of this sheet during its shaping, reduce the amount of lubricating oil to be deposited on the sheet before shaping, and improve the temporary protection against corrosion of the sheet.
- the subject of the invention is the use of an aqueous treatment solution containing sulphate ions SO 4 2- at a concentration greater than or equal to 0.01 mol / l, for treating the surface of a sheet coated steel on at least one of its faces, a metal coating based on zinc or its alloys, to reduce the formation of powder or metal particles based on zinc or its alloys generated by degradation coating during the shaping of said sheet.
- metal coating based on zinc alloy a zinc coating comprising one or more alloying elements, such as for example and without limitation, iron, aluminum, silicon, magnesium, and nickel.
- the treatment solution is conventionally applied, for example by dipping, by spraying or by coating, as well on electrogalvanized sheets as on dip galvanized sheets.
- the aqueous treatment solution additionally contains Zn 2+ ions at a concentration greater than or equal to 0.01 mol / l, which make it possible to obtain a more homogeneous deposition.
- the solution of treatment by dissolution of zinc sulphate in pure water is prepared; for example, zinc sulfate heptahydrate (ZnSO 4 , 7H 2 O) is used; the concentration of Zn 2+ ions is then equal to that of the SO 4 2- anions.
- ZnSO 4 , 7H 2 O zinc sulfate heptahydrate
- the pH of the treatment solution preferably corresponds to the natural pH of the solution, without addition of base or acid; the value of this pH is generally between 5 and 7.
- the treatment solution is applied to the surface of the sheet under conditions of temperature, time of contact with the galvanized surface, concentration of SO 4 2- ions and Zn 2+ ions adjusted to form a layer based on zinc hydroxysulfate and zinc sulphate whose sulfur content is greater or equal to 0.5 mg / m 2 .
- concentration of SO 4 2- ions and Zn 2+ ions adjusted to form a layer based on zinc hydroxysulfate and zinc sulphate whose sulfur content is greater or equal to 0.5 mg / m 2 .
- the contact time of the treatment solution with the galvanized surface is between 2 seconds and 2 minutes, and the temperature of the treatment solution is between 20 and 60 ° C.
- the treatment solution used contains between 20 and 160 g / l of zinc sulphate heptahydrate, corresponding to a concentration of Zn 2+ ions and a concentration of SO 4 2- ions of between 0.07 and 0.55 mol. / l. Indeed, it was found that in this range of concentrations, the deposition rate was little influenced by the value of the concentration.
- the treatment solution is applied under conditions of temperature, time of contact with the galvanized surface, and of concentrations of SO 4 2- ions and Zn 2+ ions adjusted to form a layer based on hydroxysulfate and sulfate having a sulfur content of between 3.7 and 27 mg / m 2 .
- the treatment solution contains an oxidizing agent for zinc, such as hydrogen peroxide.
- This oxidizing agent can have a very marked hydroxysulfation and sulphation accelerator effect at low concentration. It was found that the addition of only 0.03%, ie 8.10 -3 mol / liter of hydrogen peroxide, or 2.10 -4 mol / liter of potassium permanganate in the solution allowed to double (approximately) the speed of deposit. It has been found, on the contrary, that concentrations 100 times higher no longer made it possible to obtain this improvement in the deposition rate.
- the layer deposited on the sheet is adherent; Drying is adjusted to remove residual liquid water from the deposit.
- the sheet is preferably rinsed so as to eliminate the soluble part of the deposit obtained; the absence of rinsing and the obtaining of a partially water-soluble deposit resulting therefrom are not very detrimental to the reduction of the degradation of the galvanized coating during the shaping of the sheet, as long as the obtained deposit includes a layer based on zinc hydroxysulfate and zinc sulfate insoluble in water in contact with the sheet.
- the aqueous treatment solution comprising a concentration of SO 4 2- ions greater than or equal to 0.01 mol / l is applied under anodic polarization, and the pH of the treatment solution is greater than or equal to 12, and less than 13.
- the pH of the solution is less than 12, no adhering hydroxysulfates are formed on the surface to be treated. If the pH of the solution is greater than or equal to 13, the hydroxysulfate is redissolved and / or decomposed into zinc hydroxides.
- the concentration of SO 4 2- ions is greater than or equal to 0.01 mol per liter, and preferably greater than or equal to 0.07 mol / l.
- the concentration of sulphate ions is preferably less than or equal to 1 mol / liter; in the case of the use of sodium sulphate, at concentrations greater than 142 g / l (equivalent to 1 mol SO 4 2- / liter), for example 180 g / l, there is a decrease in the formation yield of the layer based on zinc hydroxysulfate and zinc sulfate.
- the total quantity of hydroxysulfates and sulphates deposited should be greater than or equal to 0.5 mg / m 2 and less than or equal to 30 mg / m 2 in equivalent sulfur, preferably between 3.5 and 27 mg / m 2 sulfur equivalent.
- the zinc required for the formation of the zinc hydroxysulfate and zinc sulphate deposit results from the anodic dissolution of the zinc under the effect of the polarization of the galvanized surface.
- the density of electrical charges, circulating during the treatment through the surface of the sheet be adjusted so as to form a layer based on zinc hydroxysulfate and zinc sulphate, the sulfur content is greater or equal to 0.5 mg / m 2 .
- the charge density applied is preferably between 10 and 100 C / dm 2 of surface to be treated.
- the layer based on zinc hydroxysulfate and zinc sulphate at a high polarization current density, in particular greater than 20 A / dm 2 and, for example 200 A / dm 2 .
- the deposition efficiency is very low and the amount of sulfur in the deposited layer does not make it possible to obtain a significant reduction in the degradation of the zinc coating of the sheet metal. when formatting.
- the temperature of the treatment solution is generally between 20 ° C and 60 ° C. Preferably, a temperature greater than or equal to 40 ° C. is used, so as to increase the conductivity of the solution and to reduce the ohmic losses.
- the speed of circulation of the solution at the surface of the sheet does not have a decisive impact on the treatment according to the invention.
- the treated surface is thoroughly rinsed with deionized water. This rinsing step is important for removing alkaline reagents from the deposition surface, which would cause corrosion problems.
- the lubricating oil film is applied with a grammage of preferably less than 0.9 g / m 2 , and more preferably between 0.2 and 0.5 g / m 2 , because these weights are sufficient to obtain excellent protection. temporary protection against corrosion and avoid any risk of pollution of the workshops and the tools of formatting.
- the subject of the invention is the use of an aqueous treatment solution comprising sulphate ions at a concentration greater than or equal to 0.01 mol / l, to improve the temporary protection against corrosion of a metal sheet. steel coated with a metal layer based on zinc or its alloys.
- this aqueous treatment solution to the steel sheet is carried out according to the embodiments described in the paragraphs concerning the use of an aqueous treatment solution containing sulphate ions to treat a zinc-coated steel sheet. to reduce the degradation of the zinc coating during its shaping. For this purpose, see the relevant paragraphs.
- Test specimens are cut from 0.7 mm thick ES-grade "ES-coated steel" steel sheet coated on both sides with a hot dipped zinc coating. in a bath of zinc.
- An aqueous treatment solution according to the invention prepared with 125 g / l zinc sulfate heptahydrate ZnSO 4 , 7 H 2 O was prepared.
- This treatment solution was then applied to a portion of the specimens by spraying the treatment solution at a temperature of 40 ° C. After a contact time of the solution with the sheet of 3 to 4 s, the treated sheet is dewatered and then dried.
- a film of lubricating oil which can be either QUAKER 6130 oil (from Quaker Company), which is FUCHS 4107S (from Fuchs), with a basis weight of 1.5 g / m 2 .
- test specimens not previously treated with the treatment solution according to the invention was oiled either with QUAKER 6130 oil or with FUCHS 4107S oil also with a weight of 1.5 g / m 2 .
- test pieces were then subjected to a controlled strain test by means of a press comprising a punch, a die and a blank holder, recreating in the laboratory the stresses undergone by the sheet during the stamping operation. especially in the matrix rays and / or in the retaining rings that equip the stamping tools. Different clamping forces of the blank holder were applied to the test pieces.
- the press was wiped so as to identify the powder or zinc coating particles lost by the specimen in the press.
- test pieces A portion of these test pieces is treated with a treatment solution according to the invention, under the same conditions as those indicated in Example 1, so as to form a layer based on zinc hydroxysulfate and zinc sulfate. Then a film of lubricating oil (QUAKER 6130 oil) is applied to this layer with amounts ranging from 0.25 to 2.5 g / m 2 .
- a film of lubricating oil (QUAKER 6130 oil) is applied to this layer with amounts ranging from 0.25 to 2.5 g / m 2 .
- test pieces Another part of the test pieces was oiled in the same way as before, but was not previously treated with the treatment solution according to the invention.
- Table 2 shows, for each of the test pieces tested, an average value of the coefficient of friction for a given clamping force Fs.
- ⁇ u> Table 2 ⁇ / u> Clamping force (MPa) Coefficient of friction
- Oil weight of the treated sheet according to the invention Oil weight of untreated sheet 0.25 (g / m 2 ) 1.0 (g / m 2 ) 2.5 (g / m 2 ) 0.25 (g / m 2 ) 1.0 (g / m 2 ) 2.5 (g / m 2 ) 30 0.13 0.12 0.12 0.20 0.15 0.15 50 0.11 0.11 0.11 0.20 0.17 0.17
- Test specimens are cut from 0.7 mm thick ES-grade "ES-coated steel" steel sheet coated on both sides with a hot dipped zinc coating. in a bath of zinc.
- test pieces A portion of these test pieces is treated with a treatment solution according to the invention, under the same conditions as those indicated in Example 1, so as to form a layer based on zinc hydroxysulfate and zinc sulfate. Then a film of lubricating oil (QUAKER oil 6130) with weights of between 0.25 and 1.0 g / m 2 is applied to this layer.
- a film of lubricating oil (QUAKER oil 6130) with weights of between 0.25 and 1.0 g / m 2 is applied to this layer.
- test pieces Another part of the test pieces was oiled in the same way as before, but was not previously treated with the treatment solution according to the invention.
- the lubricating oils applied to steel sheets coated with a zinc-based metal layer provide protection against corrosion during the time period between the manufacture of the sheets and their implementation, for example by stamping.
- test pieces are placed in a climatic chamber corresponding to the DIN 50017 standard, which simulates the corrosion conditions of an outer coil of sheet metal coil or sheet metal sheet during storage.
- the specimens are suspended vertically individually.
- the result of the test is obtained by recording the number of successive cycles before the appearance of corrosion on the test specimen.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Coating With Molten Metal (AREA)
- Electroplating Methods And Accessories (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0315381A FR2864552B1 (fr) | 2003-12-24 | 2003-12-24 | Traitement de surface par hydroxysulfate |
EP04816380A EP1699947A1 (de) | 2003-12-24 | 2004-12-14 | Hydroxysulfat-oberflächenbehandlung |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP04816380.2 Division | 2004-12-14 |
Publications (1)
Publication Number | Publication Date |
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EP2450470A1 true EP2450470A1 (de) | 2012-05-09 |
Family
ID=34639594
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP12000368A Ceased EP2450470A1 (de) | 2003-12-24 | 2004-12-14 | Hydroxysulfat-Oberflächenbehandlung |
EP04816380A Withdrawn EP1699947A1 (de) | 2003-12-24 | 2004-12-14 | Hydroxysulfat-oberflächenbehandlung |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
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EP04816380A Withdrawn EP1699947A1 (de) | 2003-12-24 | 2004-12-14 | Hydroxysulfat-oberflächenbehandlung |
Country Status (13)
Country | Link |
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US (1) | US20080308192A1 (de) |
EP (2) | EP2450470A1 (de) |
JP (1) | JP2007517135A (de) |
KR (1) | KR101022683B1 (de) |
CN (1) | CN1914354A (de) |
BR (1) | BRPI0418188B1 (de) |
CA (1) | CA2551492A1 (de) |
FR (1) | FR2864552B1 (de) |
MX (1) | MXPA06007253A (de) |
RU (1) | RU2371516C2 (de) |
UA (1) | UA89368C2 (de) |
WO (1) | WO2005071140A1 (de) |
ZA (1) | ZA200605133B (de) |
Cited By (2)
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WO2017121826A1 (de) | 2016-01-13 | 2017-07-20 | Sika Technology Ag | Einkomponentiger hitzehärtender epoxidklebstoff mit verbesserter haftung |
US10287665B2 (en) | 2014-06-27 | 2019-05-14 | Henkel Ag & Co. Kgaa | Dry lubricant for zinc coated steel |
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JP5239570B2 (ja) | 2007-09-04 | 2013-07-17 | Jfeスチール株式会社 | 亜鉛系めっき鋼板 |
JP5354165B2 (ja) * | 2008-01-30 | 2013-11-27 | Jfeスチール株式会社 | 亜鉛系めっき鋼板の製造方法 |
CA2742354C (en) * | 2008-12-16 | 2014-02-25 | Jfe Steel Corporation | Galvanized steel sheet and method for manufacturing the same |
JP5396921B2 (ja) * | 2009-03-06 | 2014-01-22 | Jfeスチール株式会社 | 溶融金属が表面に付着し難い亜鉛系めっき鋼板 |
JP4883240B1 (ja) | 2010-08-04 | 2012-02-22 | Jfeスチール株式会社 | 熱間プレス用鋼板およびそれを用いた熱間プレス部材の製造方法 |
JP5884151B2 (ja) | 2010-11-25 | 2016-03-15 | Jfeスチール株式会社 | 熱間プレス用鋼板およびそれを用いた熱間プレス部材の製造方法 |
PL2802682T3 (pl) * | 2012-01-10 | 2021-04-19 | Arcelormittal | Zastosowanie roztworu zawierającego jony siarczanowe w celu zmniejszenia czernienia lub matowienia blachy podczas jej przechowywania oraz blacha traktowana takim roztworem |
WO2013132816A1 (ja) | 2012-03-07 | 2013-09-12 | Jfeスチール株式会社 | 熱間プレス用鋼板、その製造方法、およびそれを用いた熱間プレス部材の製造方法 |
WO2013160566A1 (fr) | 2012-04-25 | 2013-10-31 | Arcelormittal Investigacion Y Desarrollo, S.L. | Procédé de réalisation d'une tôle à revêtements znalmg huilés et tôle correspondante. |
JP5928247B2 (ja) * | 2012-08-27 | 2016-06-01 | Jfeスチール株式会社 | 冷延鋼板およびその製造方法 |
DE102012109855B4 (de) * | 2012-10-16 | 2015-07-23 | Thyssenkrupp Steel Europe Ag | Verfahren zum Herstellen eines mit einer metallischen Korrosionsschutzschicht beschichteten Stahlprodukts |
PL2851452T3 (pl) | 2013-09-19 | 2019-10-31 | Fuchs Petrolub Se | Nieorganiczna powłoka funkcyjna na stali ocynkowanej ogniowo jako pomocna przy formowaniu |
EP2995674B1 (de) * | 2014-09-11 | 2020-07-15 | thyssenkrupp AG | Verwendung eines Sulfats sowie Verfahren zum Herstellen eines Stahlbauteils durch Umformen in einer Umformmaschine |
EP3405600B1 (de) * | 2016-01-19 | 2019-10-16 | ThyssenKrupp Steel Europe AG | Verfahren zum herstellen eines stahlprodukts mit einer zn-beschichtung und einer darauf aufgetragenen tribologisch aktiven schicht sowie entsprechend beschaffenes stahlprodukt |
KR102657200B1 (ko) | 2017-03-30 | 2024-04-12 | 타타 스틸 이즈무이덴 베.뷔. | 금속 표면 처리용 수성 산성 조성물, 이 조성물을 사용한 처리 방법, 및 처리된 금속 표면 |
WO2019073274A1 (en) | 2017-10-12 | 2019-04-18 | Arcelormittal | PROCESS FOR PROCESSING METAL SHEET AND METAL SHEET TREATED USING THE SAME |
WO2019073273A1 (en) * | 2017-10-12 | 2019-04-18 | Arcelormittal | PROCESS FOR PROCESSING METAL SHEET AND METAL SHEET TREATED WITH THIS METHOD |
EP3643759B1 (de) | 2018-10-26 | 2022-03-23 | Henkel AG & Co. KGaA | Polycarboxylat-beschichteter bandstahl und dessen verwendung zum tiefziehen |
EP3898860A1 (de) | 2018-12-19 | 2021-10-27 | Henkel AG & Co. KGaA | Umformbeschichtungsmittel, mit diesem mittel beschichteter bandstahl und dessen verwendung in der herstellung von bauteilen durch umformen |
Citations (4)
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WO2000015878A1 (fr) * | 1998-09-15 | 2000-03-23 | Sollac | Toles d'acier zingue revetues d'une couche prelubrifiante d'hydroxysulfate et procedes d'obtention de cette tole |
WO2001051682A1 (fr) * | 2000-01-13 | 2001-07-19 | Usinor | Procede d'oxalatation de la surface zinguee d'une tole |
WO2002097151A1 (fr) * | 2001-05-28 | 2002-12-05 | Kawasaki Steel Corporation | Plaque d'acier galvanise par alliage, presentant d'excellentes proprietes de glissement |
WO2005021823A1 (ja) * | 2003-08-29 | 2005-03-10 | Jfe Steel Corporation | 溶融亜鉛めっき鋼板およびその製造方法 |
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JP2001329352A (ja) * | 2000-05-19 | 2001-11-27 | Sumitomo Metal Ind Ltd | 摺動性に優れた合金化溶融亜鉛めっき鋼板 |
JP3582511B2 (ja) * | 2001-10-23 | 2004-10-27 | 住友金属工業株式会社 | 熱間プレス成形用表面処理鋼とその製造方法 |
-
2003
- 2003-12-24 FR FR0315381A patent/FR2864552B1/fr not_active Expired - Fee Related
-
2004
- 2004-12-14 RU RU2006126698/02A patent/RU2371516C2/ru not_active IP Right Cessation
- 2004-12-14 US US10/583,765 patent/US20080308192A1/en not_active Abandoned
- 2004-12-14 MX MXPA06007253A patent/MXPA06007253A/es unknown
- 2004-12-14 BR BRPI0418188-3A patent/BRPI0418188B1/pt not_active IP Right Cessation
- 2004-12-14 CN CNA2004800406185A patent/CN1914354A/zh active Pending
- 2004-12-14 KR KR1020067014952A patent/KR101022683B1/ko not_active IP Right Cessation
- 2004-12-14 WO PCT/FR2004/003208 patent/WO2005071140A1/fr active Application Filing
- 2004-12-14 CA CA002551492A patent/CA2551492A1/en not_active Abandoned
- 2004-12-14 EP EP12000368A patent/EP2450470A1/de not_active Ceased
- 2004-12-14 JP JP2006546227A patent/JP2007517135A/ja active Pending
- 2004-12-14 EP EP04816380A patent/EP1699947A1/de not_active Withdrawn
- 2004-12-14 UA UAA200608324A patent/UA89368C2/ru unknown
-
2006
- 2006-06-22 ZA ZA200605133A patent/ZA200605133B/en unknown
Patent Citations (5)
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WO2000015878A1 (fr) * | 1998-09-15 | 2000-03-23 | Sollac | Toles d'acier zingue revetues d'une couche prelubrifiante d'hydroxysulfate et procedes d'obtention de cette tole |
WO2001051682A1 (fr) * | 2000-01-13 | 2001-07-19 | Usinor | Procede d'oxalatation de la surface zinguee d'une tole |
WO2002097151A1 (fr) * | 2001-05-28 | 2002-12-05 | Kawasaki Steel Corporation | Plaque d'acier galvanise par alliage, presentant d'excellentes proprietes de glissement |
EP1391530A1 (de) * | 2001-05-28 | 2004-02-25 | JFE Steel Corporation | Galvanisierte stahlplatte mit ausgezeichneter gleiteigenschaft |
WO2005021823A1 (ja) * | 2003-08-29 | 2005-03-10 | Jfe Steel Corporation | 溶融亜鉛めっき鋼板およびその製造方法 |
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Title |
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KUNDE N D ET AL: "Correlation of prephosphate treatment, surface friction and powdering of galvanneal during forming", SAE SPEC PUBL; SAE SPECIAL PUBLICATIONS; DEVELOPMENTS IN SHEET METAL STAMPING FEB 1998 SAE, WARRENDALE, PA, USA, vol. 1322, February 1998 (1998-02-01), pages 17 - 22, XP002290602 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10287665B2 (en) | 2014-06-27 | 2019-05-14 | Henkel Ag & Co. Kgaa | Dry lubricant for zinc coated steel |
WO2017121826A1 (de) | 2016-01-13 | 2017-07-20 | Sika Technology Ag | Einkomponentiger hitzehärtender epoxidklebstoff mit verbesserter haftung |
US10738226B2 (en) | 2016-01-13 | 2020-08-11 | Sika Technology Ag | Single-component thermosetting epoxy resin with improved adhesion |
Also Published As
Publication number | Publication date |
---|---|
US20080308192A1 (en) | 2008-12-18 |
CA2551492A1 (en) | 2005-08-04 |
JP2007517135A (ja) | 2007-06-28 |
RU2371516C2 (ru) | 2009-10-27 |
KR20060129306A (ko) | 2006-12-15 |
RU2006126698A (ru) | 2008-01-27 |
FR2864552B1 (fr) | 2006-07-21 |
MXPA06007253A (es) | 2006-08-18 |
CN1914354A (zh) | 2007-02-14 |
FR2864552A1 (fr) | 2005-07-01 |
BRPI0418188A (pt) | 2007-04-27 |
EP1699947A1 (de) | 2006-09-13 |
ZA200605133B (en) | 2007-09-26 |
UA89368C2 (ru) | 2010-01-25 |
BRPI0418188B1 (pt) | 2015-08-18 |
KR101022683B1 (ko) | 2011-03-17 |
WO2005071140A1 (fr) | 2005-08-04 |
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