EP1699947A1 - Traitement de surface par hydroxysulfate - Google Patents
Traitement de surface par hydroxysulfateInfo
- Publication number
- EP1699947A1 EP1699947A1 EP04816380A EP04816380A EP1699947A1 EP 1699947 A1 EP1699947 A1 EP 1699947A1 EP 04816380 A EP04816380 A EP 04816380A EP 04816380 A EP04816380 A EP 04816380A EP 1699947 A1 EP1699947 A1 EP 1699947A1
- Authority
- 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.)
- Withdrawn
Links
- 238000004381 surface treatment Methods 0.000 title description 2
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 21
- 239000010959 steel Substances 0.000 claims abstract description 21
- 230000007797 corrosion Effects 0.000 claims abstract description 16
- 238000005260 corrosion Methods 0.000 claims abstract description 16
- 229910021653 sulphate ion Inorganic materials 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 6
- -1 sulphate ions Chemical class 0.000 claims abstract description 6
- 230000001050 lubricating effect Effects 0.000 claims abstract description 4
- 239000011701 zinc Substances 0.000 claims description 46
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 37
- 229910052725 zinc Inorganic materials 0.000 claims description 37
- 239000003921 oil Substances 0.000 claims description 32
- 239000011248 coating agent Substances 0.000 claims description 30
- 238000000576 coating method Methods 0.000 claims description 30
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 19
- 150000002500 ions Chemical class 0.000 claims description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 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
- 239000000843 powder Substances 0.000 claims description 14
- 238000007493 shaping process Methods 0.000 claims description 14
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 14
- 239000010687 lubricating oil Substances 0.000 claims description 13
- 229960001763 zinc sulfate Drugs 0.000 claims description 13
- 230000015556 catabolic process Effects 0.000 claims description 12
- 238000006731 degradation reaction Methods 0.000 claims description 12
- VCPQWWKLNIMKND-UHFFFAOYSA-L zinc hydroxy sulfate Chemical compound [Zn++].OOS([O-])(=O)=O.OOS([O-])(=O)=O VCPQWWKLNIMKND-UHFFFAOYSA-L 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 230000010287 polarization Effects 0.000 claims description 4
- 239000013528 metallic particle Substances 0.000 claims description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims 1
- 238000013034 coating degradation Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 12
- 229910001335 Galvanized steel Inorganic materials 0.000 description 8
- 239000008397 galvanized steel Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 235000009529 zinc sulphate Nutrition 0.000 description 6
- 239000011686 zinc sulphate Substances 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 241000282485 Vulpes vulpes Species 0.000 description 3
- 230000001464 adherent effect Effects 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 230000006735 deficit Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 1
- 229910000997 High-speed 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
- 229910001297 Zn alloy Inorganic materials 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
- 150000001450 anions Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 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
- 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
- 210000003739 neck Anatomy 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
- 238000005507 spraying Methods 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 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
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
- C23C22/68—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 metallic coating based on zinc or its alloys. It also relates to a method of lubricating such a coated sheet.
- Steel sheets coated with zinc or its alloys are commonly used in the automotive field and in industry in general, because they have excellent resistance to corrosion.
- these galvanized steel sheets present a certain number of difficulties when they are shaped, for example by stamping, to manufacture parts.
- a film of lubricating oil is applied to their surface which facilitates shaping.
- the very high friction exerted by the shaping tools on the surface of the sheet metal causes, on the surface of the sheet metal, powder or particles based on zinc or its alloys generated by degradation of the coating.
- the accumulation and / or agglomeration of these particles or of this powder in the shaping tools can cause damage to the formed parts, by the formation of spikes and / or necks.
- the sheet due to the high coefficient of friction which characterizes the sliding of a galvanized surface in contact with the surface of a forming tool, the sheet may break if there is insufficient sliding of the sheet in the grip of the formatting tool.
- the present invention therefore aims to provide a treatment solution which, applied to the surface of a steel sheet coated with a metallic layer based on zinc or its alloys, makes it possible to reduce the degradation of the zinc-plated surface. of this sheet during its shaping, to reduce the quantity of lubricating oil to deposit on the sheet before its shaping, and to 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 of steel coated on at least one of its faces with a metallic coating based on zinc or its alloys, in order to reduce the formation of powder or metallic particles based on zinc or its alloys generated by degradation of the coating during the shaping of said sheet.
- metallic coating based on zinc alloy means a zinc coating comprising one or more alloying elements, such as, for example and without limitation, iron, aluminum, silicon, magnesium, and nickel. According to the invention, the use of a steel sheet coated with an almost pure zinc coating is preferred.
- the treatment solution is applied in a conventional manner, for example by dipping, by sprinkling or by coating, both on electro-galvanized sheets and on galvanized sheets.
- the aqueous treatment solution also 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 deposit.
- the treatment solution is prepared, for example, by dissolving zinc sulfate in pure water; for example, zinc sulphate heptahydrate (ZnSO4, 7 H2O) is used; the concentration of Zn 2+ ions is then equal to that of the SO 4 2 7 anions.
- the pH of the treatment solution preferably corresponds to the natural pH of the solution, without the addition of base or acid; the value of this pH is generally between 5 and 7.
- concentration of SO4 2 " ions and Zn 2+ ions adjusted to form a layer based on zinc hydroxysulfate and zinc sulphate with a sulfur quantity greater than 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 solution of treatment used contains between 20 and 160 g / l of zinc sulfate heptahydrate, corresponding to a concentration of Zn 2+ ions and a concentration of SO 4 2 " ions between 0.07 and 0.55 mol / l. Indeed, it was found that, in this concentration range, 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 concentrations of SO4 2 " ions and of Zn 2+ ions adjusted to form a layer based on hydroxysulphate and sulphate having a quantity of sulfur 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 an accelerating effect on hydroxysulfation and very marked sulfation at low concentration. It has been found that the addition of only 0.03% , that is to say 8.10 "3 mol / liter of hydrogen peroxide, or of 2.10 " 4 mole / liter of potassium permanganate in the solution made it possible to double (approximately) the rate of deposition. It was found, on the contrary, that concentrations 100 times higher no longer allowed this improvement in the deposition rate to be obtained.
- the layer deposited on the sheet is adherent;
- the drying is adjusted to remove the residual liquid water between the application step and the drying step, the sheet is preferably rinsed so as to remove the soluble part of the deposit obtained; the absence of rinsing and obtaining a deposit which is partially soluble in water which results therefrom are not very detrimental to the reduction of the degradation of the zinc-plated coating during the shaping of the sheet, as long as the deposit obtained 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 2 " ions greater than or equal to 0.01 mol / l is applied under anodic polarization, and the pH of the treatment solution is higher or equal to 12, and less than 13. If the pH of the solution is less than 12, no adherent hydroxysulfates are formed on the surface to be treated. If the pH of the solution is greater than or equal to 13, the hydroxysulfate redissolves and / or decomposes into zinc hydroxides.
- the concentration of SO 4 2 " ions be greater than or equal to 0.01 moles per liter, and preferably greater than or equal to 0.07 mol / l.
- the ion concentration sulfates is preferably less than or equal to 1 mole / liter; in the case of the use of sodium sulfate, at concentrations greater than 142 g / l (equivalent to 1 mole SO 4 2 " / liter), for example 180 g / l, there is a decrease in the yield of formation of the layer based on zinc hydroxysulfate and zinc sulfate.
- the total amount of hydroxysulphates 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 sulfur equivalent, preferably between 3.5 and 27 mg / m 2 in sulfur equivalent.
- the zinc necessary for the formation of the deposit based on zinc hydroxysulphate and zinc sulphate comes from the anodic dissolution of zinc under the effect of the polarization of the zinc-plated surface. It is therefore appropriate that 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 on zinc sulfate with a higher sulfur content.
- the charge density applied is preferably between 10 and 100 C / dm 2 of surface to be treated. If the charge density exceeds 100 C / dm 2 , it can be seen that the quantity of sulfur deposited on the surface no longer increases and even decreases. Thanks to the anodic polarization of the zinc-plated surface to be treated, there is a rapid dissolution of the zinc in the immediate vicinity of the zinc-plated surface, which promotes the precipitation of zinc salts on this surface. Thus, to carry out this treatment as productively as possible with a satisfactory faradic yield, it is advisable to deposit the layer based on zinc hydroxysulfate and zinc sulfate under a high bias current density, in particular greater than 20
- 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. during its shaping.
- a titanium cathode can be used as a counter electrode.
- the temperature of the treatment solution is generally between 20 ° C and 60 ° C. Preferably, the temperature is greater than or equal to 40 ° C., so as to increase the conductivity of the solution and to reduce the ohmic losses.
- the speed of circulation of the solution on the surface of the sheet does not, here, have a decisive effect on the treatment according to the invention.
- the treated surface is thoroughly rinsed with demineralized water. This rinsing step is important to remove alkaline reagents from the surface of the deposit, which would cause corrosion problems.
- the invention also relates to a method of lubricating a steel sheet coated with a layer consisting of a metallic coating based on zinc or its alloys, and in which: - said sheet is coated with a layer upper based on zinc hydroxysulphate and zinc sulphate, said upper layer having been obtained by the use of a treatment solution according to the invention, then - a film of lubricating oil is applied to the upper layer with a grammage of less than 1 g / m 2 .
- the film of lubricating oil is applied with a grammage preferably less than 0.9 g / m 2 , and more preferably between 0.2 and 0.5 g / m 2 , because these grammages are sufficient to obtain excellent protection temporary against corrosion and avoid any risk of pollution of workshops and shaping tools.
- 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 sheet of steel coated with a metallic 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 galvanized steel sheet. to reduce the degradation of the zinc coating during its shaping.
- an aqueous treatment solution containing sulphate ions to treat a galvanized steel sheet. to reduce the degradation of the zinc coating during its shaping.
- the inventors have shown that temporary protection against corrosion of a galvanized steel sheet first treated with a treatment solution according to the invention, then coated with a film of oil was much superior to that of a galvanized steel sheet not previously treated.
- An aqueous treatment solution was prepared in accordance with the invention, prepared with 125 g / l zinc sulfate heptahydrate ZnS ⁇ 4 , 7 H 2 O. This treatment solution was then applied to part of the test pieces by spraying the solution treatment, 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 wrung and then dried. Then was applied to the layer based on zinc hydroxysulphate and zinc sulphate formed on the surface of the test pieces of galvanized steel sheet, a film of lubricating oil which may be either QUAKER 6130 oil (from Quaker company), i.e.
- FUCHS 4107S oil (from Fuchs company), with a grammage of 1.5 g / m 2 .
- Another part of the test pieces which had not been 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 grammage of 1.5 g / m 2 .
- the two series of test pieces were then subjected to a deformation test controlled by means of a press comprising a punch, a matrix and a blank holder, recreating in the laboratory the stresses undergone by the sheet during the stamping operation, in particular in the matrix radii and / or in the retaining rods which equip the stamping tools. Different clamping forces of the blank holder were applied to the test pieces tested.
- test pieces of the two series were weighed before the oiling operation, then at the end of the test after oil removal, using a balance accurate to 0.0001 grams.
- the difference in measured mass was reduced to a loss of mass per square meter, taking into account the surface affected by friction during the simulation of the stamping of the test piece, identical for each of the test pieces.
- the press was wiped so as to identify the powder or particles of zinc coating lost by the test piece in the press.
- Table 1 The results of loss of mass of the test pieces after stamping, as well as the identification of the powder and / or of the zinc particles resulting from the coating are grouped in Table 1.
- test pieces Part 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 quantities of between 0.25 and 2.5 g / m 2 . Another part of the test pieces was oiled in the same way as above, but was not previously treated with the treatment solution according to the invention. Then the friction characterization of each of the test pieces is carried out using a tribology test apparatus, in the following manner: The test apparatus is a plane-plane tribometer known in itself.
- the test pieces to be tested are clamped according to a clamping force Fs between two high-speed steel plates providing a bearing (or sliding) surface on the test pieces.
- the coefficient of friction N is measured, while moving the test piece relative to the pads over a total stroke D of 180 mm and at the speed of 10 mm / Fs by gradually increasing the clamping force Fs.
- test pieces Part 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 grammages between 0.25 and 1.0 g / m 2 . Another part of the test pieces was oiled in the same way as above, 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 guarantee protection against corrosion during the period of time between the manufacture of the sheets and their implementation, for example by stamping.
- test specimens 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 of a sheet metal cut into sheets during storage.
- the test pieces are individually hung vertically.
- the test result, shown in table 3 is obtained by recording the number of successive cycles before the corrosion traces appear on the test piece.
Landscapes
- 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)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
- Coating With Molten Metal (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP12000368A EP2450470A1 (fr) | 2003-12-24 | 2004-12-14 | Traitement de surface par hydroxysultate |
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 |
PCT/FR2004/003208 WO2005071140A1 (fr) | 2003-12-24 | 2004-12-14 | Traitement de surface par hydroxysulfate |
Publications (1)
Publication Number | Publication Date |
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EP1699947A1 true EP1699947A1 (fr) | 2006-09-13 |
Family
ID=34639594
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP12000368A Ceased EP2450470A1 (fr) | 2003-12-24 | 2004-12-14 | Traitement de surface par hydroxysultate |
EP04816380A Withdrawn EP1699947A1 (fr) | 2003-12-24 | 2004-12-14 | Traitement de surface par hydroxysulfate |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP12000368A Ceased EP2450470A1 (fr) | 2003-12-24 | 2004-12-14 | Traitement de surface par hydroxysultate |
Country Status (13)
Country | Link |
---|---|
US (1) | US20080308192A1 (fr) |
EP (2) | EP2450470A1 (fr) |
JP (1) | JP2007517135A (fr) |
KR (1) | KR101022683B1 (fr) |
CN (1) | CN1914354A (fr) |
BR (1) | BRPI0418188B1 (fr) |
CA (1) | CA2551492A1 (fr) |
FR (1) | FR2864552B1 (fr) |
MX (1) | MXPA06007253A (fr) |
RU (1) | RU2371516C2 (fr) |
UA (1) | UA89368C2 (fr) |
WO (1) | WO2005071140A1 (fr) |
ZA (1) | ZA200605133B (fr) |
Cited By (1)
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 |
Families Citing this family (20)
Publication number | Priority date | Publication date | Assignee | Title |
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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 (fr) * | 2008-12-16 | 2014-02-25 | Jfe Steel Corporation | Tole d'acier galvanise et son procede de production |
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 |
WO2013104835A1 (fr) * | 2012-01-10 | 2013-07-18 | Arcelormittal Investigación Y Desarrollo Sl | Utilisation d'une solution contenant des ions sulfates pour reduire le noircissement ou le ternissement d'une tole lors de son stockage et tole traitee par une telle solution. |
CN104136650B (zh) | 2012-03-07 | 2017-04-19 | 杰富意钢铁株式会社 | 热压用钢板、其制造方法和使用该热压用钢板的热压部件的制造方法 |
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 (fr) * | 2014-09-11 | 2020-07-15 | thyssenkrupp AG | Utilisation d'un sulfate et procede pour la production d'un élément en acier par formage dans une machine de formage |
JP2019507214A (ja) | 2016-01-13 | 2019-03-14 | シーカ テクノロジー アクチェンゲゼルシャフト | 改善された接着性を有する単一成分熱硬化性エポキシ樹脂 |
JP6629979B2 (ja) * | 2016-01-19 | 2020-01-15 | ティッセンクルップ スチール ヨーロッパ アクチェンゲゼルシャフトThyssenKrupp Steel Europe AG | Znコーティングおよびこのコーティングに堆積されたトライボロジー活性層を有する鋼製品を製造する方法、およびこの方法に従って製造された鋼製品 |
WO2018178108A1 (fr) | 2017-03-30 | 2018-10-04 | Tata Steel Ijmuiden B.V. | Composition acide aqueuse pour le traitement des surfaces métalliques, procédé de traitement l'utilisant et utilisation de la surface métallique traitée |
WO2019073273A1 (fr) | 2017-10-12 | 2019-04-18 | Arcelormittal | Procédé de traitement de feuille métallique et feuille métallique traitée avec ce procédé |
WO2019073274A1 (fr) * | 2017-10-12 | 2019-04-18 | Arcelormittal | Procédé de traitement de feuille métallique et feuille métallique traitée à l'aide de ce procédé |
EP3643759B1 (fr) | 2018-10-26 | 2022-03-23 | Henkel AG & Co. KGaA | Acier à feuillard revêtu de polycarboxylate et son utilisation pour l'emboutissage |
EP3898860A1 (fr) | 2018-12-19 | 2021-10-27 | Henkel AG & Co. KGaA | Agent de revêtement de formage, feuillard d'acier revêtu de cet agent et son utilisation dans la fabrication de pièces par formage |
Citations (1)
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WO2005021823A1 (fr) * | 2003-08-29 | 2005-03-10 | Jfe Steel Corporation | Tole d'acier plaquee de zinc par immersion a chaud et procede de production de cette tole |
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FR2783256B1 (fr) * | 1998-09-15 | 2000-10-27 | Lorraine Laminage | Traitement anodique de toles d'acier zingue dans des solutions aqueuses contenant des sulfates |
FR2803855B1 (fr) * | 2000-01-13 | 2002-05-31 | Usinor | Procede d'oxalatation de la surface zinguee d'une tole |
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 |
CN1443251A (zh) * | 2001-05-28 | 2003-09-17 | 川崎制铁株式会社 | 滑动性出色的热浸镀锌合金钢板 |
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 |
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2003
- 2003-12-24 FR FR0315381A patent/FR2864552B1/fr not_active Expired - Fee Related
-
2004
- 2004-12-14 EP EP12000368A patent/EP2450470A1/fr not_active Ceased
- 2004-12-14 US US10/583,765 patent/US20080308192A1/en not_active Abandoned
- 2004-12-14 WO PCT/FR2004/003208 patent/WO2005071140A1/fr active Application Filing
- 2004-12-14 JP JP2006546227A patent/JP2007517135A/ja active Pending
- 2004-12-14 KR KR1020067014952A patent/KR101022683B1/ko not_active IP Right Cessation
- 2004-12-14 BR BRPI0418188-3A patent/BRPI0418188B1/pt active IP Right Grant
- 2004-12-14 UA UAA200608324A patent/UA89368C2/ru unknown
- 2004-12-14 MX MXPA06007253A patent/MXPA06007253A/es unknown
- 2004-12-14 EP EP04816380A patent/EP1699947A1/fr not_active Withdrawn
- 2004-12-14 CA CA002551492A patent/CA2551492A1/fr not_active Abandoned
- 2004-12-14 CN CNA2004800406185A patent/CN1914354A/zh active Pending
- 2004-12-14 RU RU2006126698/02A patent/RU2371516C2/ru not_active IP Right Cessation
-
2006
- 2006-06-22 ZA ZA200605133A patent/ZA200605133B/en unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005021823A1 (fr) * | 2003-08-29 | 2005-03-10 | Jfe Steel Corporation | Tole d'acier plaquee de zinc par immersion a chaud et procede de production de cette tole |
EP1666624A1 (fr) * | 2003-08-29 | 2006-06-07 | JFE Steel Corporation | Tole d'acier plaquee de zinc par immersion a chaud et procede de production de cette tole |
Cited By (1)
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 |
Also Published As
Publication number | Publication date |
---|---|
CN1914354A (zh) | 2007-02-14 |
FR2864552A1 (fr) | 2005-07-01 |
BRPI0418188B1 (pt) | 2015-08-18 |
EP2450470A1 (fr) | 2012-05-09 |
CA2551492A1 (fr) | 2005-08-04 |
KR20060129306A (ko) | 2006-12-15 |
ZA200605133B (en) | 2007-09-26 |
MXPA06007253A (es) | 2006-08-18 |
BRPI0418188A (pt) | 2007-04-27 |
WO2005071140A1 (fr) | 2005-08-04 |
RU2006126698A (ru) | 2008-01-27 |
FR2864552B1 (fr) | 2006-07-21 |
KR101022683B1 (ko) | 2011-03-17 |
UA89368C2 (ru) | 2010-01-25 |
JP2007517135A (ja) | 2007-06-28 |
US20080308192A1 (en) | 2008-12-18 |
RU2371516C2 (ru) | 2009-10-27 |
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