US20080308192A1 - Hydroxysulfate Surface Treatment - Google Patents
Hydroxysulfate Surface Treatment Download PDFInfo
- Publication number
- US20080308192A1 US20080308192A1 US10/583,765 US58376504A US2008308192A1 US 20080308192 A1 US20080308192 A1 US 20080308192A1 US 58376504 A US58376504 A US 58376504A US 2008308192 A1 US2008308192 A1 US 2008308192A1
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- US
- United States
- Prior art keywords
- sheet
- zinc
- treatment solution
- sulfate
- less
- 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.)
- Abandoned
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- 238000004381 surface treatment Methods 0.000 title 1
- 239000011248 coating agent Substances 0.000 claims abstract description 31
- 238000000576 coating method Methods 0.000 claims abstract description 31
- 230000007797 corrosion Effects 0.000 claims abstract description 16
- 238000005260 corrosion Methods 0.000 claims abstract description 16
- 230000015556 catabolic process Effects 0.000 claims abstract description 12
- 238000006731 degradation reaction Methods 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 8
- 230000001050 lubricating effect Effects 0.000 claims abstract description 5
- 239000003921 oil Substances 0.000 claims description 42
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 32
- 239000011701 zinc Substances 0.000 claims description 31
- 229910052725 zinc Inorganic materials 0.000 claims description 31
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 20
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 20
- 229910000831 Steel Inorganic materials 0.000 claims description 19
- 239000010959 steel Substances 0.000 claims description 19
- 229960001763 zinc sulfate Drugs 0.000 claims description 18
- 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
- 239000002245 particle 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
- 239000000843 powder Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- -1 Zn2+ ions Chemical class 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 230000010287 polarization Effects 0.000 claims description 6
- 229910001335 Galvanized steel Inorganic materials 0.000 abstract description 9
- 239000008397 galvanized steel Substances 0.000 abstract description 9
- 238000000151 deposition Methods 0.000 description 7
- 230000008021 deposition Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 241000282485 Vulpes vulpes Species 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910000655 Killed steel Inorganic materials 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 230000001464 adherent effect Effects 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
- 230000004580 weight loss Effects 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
- 238000011109 contamination Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000011686 zinc sulphate Substances 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
- 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
- 238000004140 cleaning Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000005237 degreasing agent Methods 0.000 description 1
- 230000007613 environmental effect Effects 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
- 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
- 238000003860 storage Methods 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction 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
- 238000009827 uniform distribution Methods 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
- a film of lubricating oil is applied to its surface so as to facilitate the forming operation.
- the oil deficiency in certain areas of the oil film due to the dewetting effect is also responsible for lesser temporary corrosion protection of the steel sheet while it is being stored.
- the subject of the invention is the use of an aqueous treatment solution containing sulfate ions SO 4 2 ⁇ with a concentration of not less than 0.01 mol/l in order to treat the surface of a steel sheet treated on at least one of its sides with a metal coating based on zinc or its alloys, for the purpose of reducing the formation of metal powder or particles based on zinc or its alloys generated by the degradation of the coating while said sheet is being formed.
- the use of a steel sheet coated with an almost pure zinc coating is preferred.
- a layer forms on the surface of the sheet that is based on zinc hydroxysulfate and zinc sulfate and is both sufficiently thick and sufficiently adherent.
- SO 4 2 ⁇ concentration is less than 0.01 mol/l, but it has also been found that too high a concentration does not substantially improve the rate of deposition and may even slightly reduce it.
- the treatment solution is applied in a conventional manner, for example by dipping, by spraying or by coating, both on electrogalvanized sheet and on hot-dip galvanized sheet.
- the conditions under which the treatment solution is applied to the surface of the sheet namely the temperature, the time during which the solution is in contact with the galvanized surface, the SO 4 2 ⁇ ion concentration and the Zn 2+ ion concentration, are adjusted so as to form a layer based on zinc hydroxysulfate and zinc sulfate, the sulfur content of which is not less than 0.5 mg/m 2 . This is because when the sulfur content is less than 0.5 mg/m 2 , the reduction in degradation of the coating is less substantial.
- the time during which the treatment solution is in contact with the galvanized surface is between two seconds and two 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 sulfate heptahydrate, which corresponds to a Zn 2+ ion concentration and an SO 4 2 ⁇ ion concentration that lie between 0.07 and 0.55 mol/l.
- zinc sulfate heptahydrate which corresponds to a Zn 2+ ion concentration and an SO 4 2 ⁇ ion concentration that lie between 0.07 and 0.55 mol/l.
- the treatment solution contains an oxidizing agent for zinc, such as hydrogen peroxide.
- This oxidizing agent may have a very pronounced sulfation/hydroxysulfation accelerator effect at low concentration. It has been found that the addition of only 0.03%, i.e. 8 ⁇ 10 ⁇ 3 mol/l of hydrogen peroxide, or of 2 ⁇ 10 ⁇ 4 mol/l of potassium permanganate, to the solution makes it possible for the rate of deposition to be doubled (approximately). However, it has been found that concentrations 100 times higher no longer allow this improvement in deposition rate to be obtained.
- the layer deposited on the sheet is adherent.
- the drying is adjusted in order to remove the residual liquid water from the deposit.
- the aqueous treatment solution having an SO 4 2 ⁇ ion concentration of not less than 0.01 mol/l is applied under anodic polarization and the pH of the treatment solution is equal to 12 or higher, but less than 13.
- the pH of the solution is less than 12, adherent hydroxysulfates are not formed on the surface to be treated. If the pH of the solution is equal to 13 or higher, the hydroxysulfate redissolves and/or decomposes into zinc hydroxides.
- the thickness of the zinc hydroxysulfate/zinc sulfate-based layer deposited corresponds to more than 0.5 mg/m 2 of equivalent sulfur, preferably at least 3.5 mg/m 2 of equivalent sulfur.
- the total deposited amount of hydroxysulfates and sulfates is not less than 0.5 mg/m 2 but not to exceed 30 mg/m 2 of equivalent sulfur, preferably to be between 3.5 and 27 mg/m 2 of equivalent sulfur.
- the zinc needed to form the zinc hydroxysulfate/zinc sulfate-based deposit comes from the anodic dissolution of zinc under the effect of the polarization of the galvanized surface.
- the applied charge density is preferably between 10 and 100 C/dm 2 of surface to be treated.
- the zinc hydroxy-sulfate/zinc sulfate-based layer to be deposited under a high polarization current density, especially greater than 20 A/dm 2 , 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 significantly reduce the degradation of the zinc coating on the sheet while it is being formed.
- the temperature of the treatment solution is generally between 20° C. and 60° C.
- the treatment is carried out at a temperature of 40° C. or higher, so as to increase the conductivity of the solution and to reduce the ohmic losses.
- the coated surface is thoroughly rinsed with demineralized water. This rinsing step is important in order to remove the alkaline reactants at the surface of the deposit, reactants that might cause corrosion problems.
- the subject of the invention is also a method of lubricating a steel sheet coated with a layer consisting of a metal coating based on zinc or its alloys, in which method:
- the weight of lubricating oil film applied is preferably less than 0.9 g/m 2 and is more particularly between 0.2 and 0.5 g/m 2 , since such weights are sufficient to obtain excellent temporary corrosion protection and to avoid any risk of contamination of workshops and forming tools.
- the subject of the invention is the use of an aqueous treatment solution comprising sulfate ions with a concentration of not less than 0.01 mol/l, in order to improve temporary corrosion protection of a steel sheet coated with a metal layer based on zinc or its alloys.
- This aqueous treatment solution is applied to the steel sheet according to the embodiments described in the paragraphs relating to the use of an aqueous treatment solution containing sulfate ions for treating a galvanized steel sheet for the purpose of reducing degradation of the zinc coating while the sheet is being formed.
- the reader may refer to the paragraphs relating thereto.
- the inventors have shown that the temporary corrosion protection of a galvanized steel sheet firstly treated with a treatment solution according to the invention and then coated with an oil film is very much better than that of a galvanized steel sheet that has not been treated beforehand.
- FIG. 1 illustrates the results of the friction tests carried out on various sheet test pieces treated according to the invention or untreated;
- FIG. 2 illustrates the results of the hot/wet corrosion tests carried out on various sheet test pieces according to the invention or untreated.
- Test pieces were cut from a steel sheet, of “aluminum-killed steel” grade and of ES quality, with a thickness of 0.7 mm and coated on each of its sides with a zinc coating produced by hot dipping in a zinc bath.
- An aqueous treatment solution according to the invention obtained from 125 g/l of zinc sulfate heptahydrate ZnSO 4 ⁇ 7H 2 O was prepared.
- this treatment solution was applied to some of the test pieces by spraying the treatment solution at a temperature of 40° C. After the sheet was in contact with the solution for a time of 3 to 4 s, the treated sheet was drained and then dried.
- a lubricating oil film was then applied to the zinc hydroxysulfate/zinc sulfate-based layer formed on the surface of the galvanized steel sheet test pieces, said oil being either QUAKER 6130 oil (from Quaker) or FUCHS 4107S oil (from Fuchs), with a film weight of 1.5 g/m 2 .
- test pieces that had not been pretreated with the treatment solution according to the invention were oiled, either with the QUAKER 6130 oil or with the FUCHS 4107S oil, again with a film weight of 1.5 g/m 2 .
- test pieces were then subjected to a controlled deformation 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 a drawing operation, especially in the die radii and/or in the retaining rings with which the drawing tools are equipped.
- Various blank-holder clamping forces were applied to the test pieces undergoing the test.
- test pieces of the two series were weighed before the oiling operation and then at the end of the test, after de-oiling, by means of a balance accurate to 0.0001 grams.
- the measured difference in weight was normalized to a weight loss per square meter, taking into account the area affected by the friction during the simulation of drawing the test piece, which was identical for each of the test pieces.
- the press was wiped so as to identify the zinc coating powder or particles lost by the test piece in the press.
- the weight loss results of the test pieces after drawing and the identification of zinc powder and/or particles coming from the coating are given in Table 1.
- the particles and/or powder are identified by a rating in the following manner, according to a scale ranging from 1 to 4, where:
- Test pieces 1 cm 2 in area were cut from a steel sheet, of “aluminum-killed steel” grade and of ES quality, with a thickness of 0.7 mm and coated on each of its sides with a zinc coating produced by hot dipping in a zinc bath.
- test pieces were treated with a treatment solution according to the invention, under the same conditions as those indicated in Example 1, so as to form a zinc hydroxysulfate/zinc sulfate-based layer.
- a lubricating oil film (QUAKER 6130 oil) is then applied to this layer in amounts ranging between 0.25 and 2.5 g/m 2 .
- test pieces were oiled in the same manner as previously, but without having been pretreated with the treatment solution according to the invention.
- the tester was a flat-on-flat tribometer known per se.
- the test pieces to be tested were clamped with a clamping force F c between two high-speed steel plates offering a bearing (or sliding) surface to the test pieces.
- the friction coefficient N was measured while moving the test piece relative to the plates over a total travel D of 180 mm and at a speed of 10 nm/s, while progressively increasing the clamping force F c .
- a curve showing the variation in friction coefficient as a function of the clamping force F c for different lubricating oil film weights can then be plotted (see FIG. 1 ).
- Test pieces were cut from a steel sheet, of “aluminum-killed steel” grade and of ES quality, with a thickness of 0.7 mm and coated on each of its sides with a zinc coating produced by hot dipping in a zinc bath.
- test pieces were treated with a treatment solution according to the invention, under the same conditions as those indicated in Example 1, so as to form a zinc hydroxysulfate/zinc sulfate-based layer.
- a lubricating oil film (QUAKER 6130 oil) was then applied to this layer in weights ranging between 0.25 and 1.0 g/m 2 .
- test pieces were oiled in the same manner as previously, but without having been pretreated with the treatment solution according to the invention.
- the lubricating oils applied to the steel sheets coated with the zinc-based metal coating guaranteed corrosion protection during the period of time that elapsed between manufacture of the sheets and their processing, for example by drawing.
- test pieces to be tested were placed in an environmental chamber corresponding to the DIN 50017 standard, which simulates the conditions for corrosion of the external turn of a coil of sheet or of an individual cut sheet during storage.
- test pieces were suspended vertically.
- a curve showing the variation in the percentage content of white rust as a function of the number of cycles for each of the test pieces tested can then be plotted (cf. FIG. 2 ).
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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 And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0315381 | 2003-12-24 | ||
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 |
---|---|
US20080308192A1 true US20080308192A1 (en) | 2008-12-18 |
Family
ID=34639594
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/583,765 Abandoned US20080308192A1 (en) | 2003-12-24 | 2004-12-14 | Hydroxysulfate Surface Treatment |
Country Status (13)
Country | Link |
---|---|
US (1) | US20080308192A1 (pt) |
EP (2) | EP1699947A1 (pt) |
JP (1) | JP2007517135A (pt) |
KR (1) | KR101022683B1 (pt) |
CN (1) | CN1914354A (pt) |
BR (1) | BRPI0418188B1 (pt) |
CA (1) | CA2551492A1 (pt) |
FR (1) | FR2864552B1 (pt) |
MX (1) | MXPA06007253A (pt) |
RU (1) | RU2371516C2 (pt) |
UA (1) | UA89368C2 (pt) |
WO (1) | WO2005071140A1 (pt) |
ZA (1) | ZA200605133B (pt) |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100255341A1 (en) * | 2007-09-04 | 2010-10-07 | Jfe Steel Corporation | Zinc-based metal plated steel sheet |
US20110226387A1 (en) * | 2008-01-30 | 2011-09-22 | Jfe Steel Corporation | Galvanized steel sheet and method for manufacturing the same |
WO2015197430A1 (en) * | 2014-06-27 | 2015-12-30 | Henkel Ag & Co. Kgaa | Dry lubricant for zinc coated steel |
WO2018178108A1 (en) | 2017-03-30 | 2018-10-04 | Tata Steel Ijmuiden B.V. | Aqueous acidic composition for treating metal surfaces, treating method using this composition and use of treated metal surface |
US10253386B2 (en) | 2012-03-07 | 2019-04-09 | Jfe Steel Corporation | Steel sheet for hot press-forming, method for manufacturing the same, and method for producing hot press-formed parts using the same |
WO2019073319A1 (en) * | 2017-10-12 | 2019-04-18 | Arcelormittal | PROCESS FOR PROCESSING METAL SHEET AND METAL SHEET TREATED WITH THIS METHOD |
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US11078573B2 (en) * | 2016-01-19 | 2021-08-03 | Thyssenkrupp Ag | Method for producing a steel product with a Zn coating and a tribologically active layer deposited on the coating, and a steel product produced according to said method |
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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 |
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- 2004-12-14 BR BRPI0418188-3A patent/BRPI0418188B1/pt not_active IP Right Cessation
- 2004-12-14 WO PCT/FR2004/003208 patent/WO2005071140A1/fr active Application Filing
- 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 KR KR1020067014952A patent/KR101022683B1/ko not_active IP Right Cessation
- 2004-12-14 EP EP12000368A patent/EP2450470A1/fr not_active Ceased
- 2004-12-14 CA CA002551492A patent/CA2551492A1/en not_active Abandoned
- 2004-12-14 JP JP2006546227A patent/JP2007517135A/ja active Pending
- 2004-12-14 CN CNA2004800406185A patent/CN1914354A/zh active Pending
- 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
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US6528182B1 (en) * | 1998-09-15 | 2003-03-04 | Sollac | Zinc coated steel plates coated with a pre-lubricating hydroxysulphate layer and methods for obtaining same |
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US20100255341A1 (en) * | 2007-09-04 | 2010-10-07 | Jfe Steel Corporation | Zinc-based metal plated steel sheet |
US8221900B2 (en) | 2007-09-04 | 2012-07-17 | Jfe Steel Corporation | Zinc-based metal plated steel sheet |
US8623514B2 (en) | 2007-09-04 | 2014-01-07 | Jfe Steel Corporation | Zinc-based metal plated steel sheet |
USRE45821E1 (en) | 2007-09-04 | 2015-12-22 | Jfe Steel Corporation | Zinc-based metal plated steel sheet |
US20110226387A1 (en) * | 2008-01-30 | 2011-09-22 | Jfe Steel Corporation | Galvanized steel sheet and method for manufacturing the same |
US10704157B2 (en) | 2012-01-10 | 2020-07-07 | ArcelorMittal Investigación y Desarrollo, S.L. | Solution for reducing the blackening or tarnishing of a metal sheet and metal sheet |
US10253386B2 (en) | 2012-03-07 | 2019-04-09 | Jfe Steel Corporation | Steel sheet for hot press-forming, method for manufacturing the same, and method for producing hot press-formed parts using the same |
US10294558B2 (en) | 2012-04-25 | 2019-05-21 | Arcelormittal Investigacion Y Desarrollo, S.L. | Method for producing a metal sheet having oiled Zn—Al—Mg coatings, and corresponding metal sheet |
US10865483B2 (en) | 2012-04-25 | 2020-12-15 | Arcelormittal | Metal sheet having oiled Zn—Al—Mg coatings |
US10287665B2 (en) | 2014-06-27 | 2019-05-14 | Henkel Ag & Co. Kgaa | Dry lubricant for zinc coated steel |
EP3161176B1 (en) | 2014-06-27 | 2018-12-19 | Henkel AG & Co. KGaA | Dry lubricant for zinc coated steel |
WO2015197430A1 (en) * | 2014-06-27 | 2015-12-30 | Henkel Ag & Co. Kgaa | Dry lubricant for zinc coated steel |
US11078573B2 (en) * | 2016-01-19 | 2021-08-03 | Thyssenkrupp Ag | Method for producing a steel product with a Zn coating and a tribologically active layer deposited on the coating, and a steel product produced according to said method |
WO2018178108A1 (en) | 2017-03-30 | 2018-10-04 | Tata Steel Ijmuiden B.V. | Aqueous acidic composition for treating metal surfaces, treating method using this composition and use of treated metal surface |
US11453947B2 (en) | 2017-03-30 | 2022-09-27 | Tata Steel Ijmuiden B.V. | Aqueous acidic composition for treating metal surfaces, treating method using this composition and use of treated metal surface |
WO2019073273A1 (en) * | 2017-10-12 | 2019-04-18 | Arcelormittal | PROCESS FOR PROCESSING METAL SHEET AND METAL SHEET TREATED WITH THIS METHOD |
CN111133123A (zh) * | 2017-10-12 | 2020-05-08 | 安赛乐米塔尔公司 | 金属板处理方法和用该方法处理的金属板 |
WO2019073274A1 (en) * | 2017-10-12 | 2019-04-18 | Arcelormittal | PROCESS FOR PROCESSING METAL SHEET AND METAL SHEET TREATED USING THE SAME |
WO2019073320A1 (en) * | 2017-10-12 | 2019-04-18 | Arcelormittal | PROCESS FOR PROCESSING METAL SHEET AND METAL SHEET PROCESSED THEREBY |
US11319631B2 (en) | 2017-10-12 | 2022-05-03 | Arcelormittal | Metal sheet treatment method and metal sheet treated with this method |
US11319633B2 (en) * | 2017-10-12 | 2022-05-03 | Arcelormittal | Metal sheet treatment method and metal sheet treated with this method |
WO2019073319A1 (en) * | 2017-10-12 | 2019-04-18 | Arcelormittal | PROCESS FOR PROCESSING METAL SHEET AND METAL SHEET TREATED WITH THIS METHOD |
WO2020083645A1 (de) | 2018-10-26 | 2020-04-30 | Henkel Ag & Co. Kgaa | Polycarboxylat-beschichteter bandstahl und dessen verwendung zum tiefziehen |
EP3643759A1 (de) | 2018-10-26 | 2020-04-29 | Henkel AG & Co. KGaA | Polycarboxylat-beschichteter bandstahl und dessen verwendung zum tiefziehen |
WO2020126518A1 (de) | 2018-12-19 | 2020-06-25 | Henkel Ag & Co. Kgaa | Umformbeschichtungsmittel, mit diesem mittel beschichteter bandstahl und dessen verwendung in der herstellung von bauteilen durch umformen |
Also Published As
Publication number | Publication date |
---|---|
KR20060129306A (ko) | 2006-12-15 |
CA2551492A1 (en) | 2005-08-04 |
EP2450470A1 (fr) | 2012-05-09 |
WO2005071140A1 (fr) | 2005-08-04 |
CN1914354A (zh) | 2007-02-14 |
FR2864552B1 (fr) | 2006-07-21 |
RU2371516C2 (ru) | 2009-10-27 |
ZA200605133B (en) | 2007-09-26 |
JP2007517135A (ja) | 2007-06-28 |
BRPI0418188B1 (pt) | 2015-08-18 |
RU2006126698A (ru) | 2008-01-27 |
FR2864552A1 (fr) | 2005-07-01 |
BRPI0418188A (pt) | 2007-04-27 |
EP1699947A1 (fr) | 2006-09-13 |
KR101022683B1 (ko) | 2011-03-17 |
UA89368C2 (ru) | 2010-01-25 |
MXPA06007253A (es) | 2006-08-18 |
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