EP2391742A1 - Procédé de revêtement de diffusion de zinc - Google Patents
Procédé de revêtement de diffusion de zincInfo
- Publication number
- EP2391742A1 EP2391742A1 EP10702601A EP10702601A EP2391742A1 EP 2391742 A1 EP2391742 A1 EP 2391742A1 EP 10702601 A EP10702601 A EP 10702601A EP 10702601 A EP10702601 A EP 10702601A EP 2391742 A1 EP2391742 A1 EP 2391742A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- zinc
- liquid
- substrate
- heat treatment
- ppm
- 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- Withdrawn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
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000011701 zinc Substances 0.000 title claims abstract description 72
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 72
- 238000009792 diffusion process Methods 0.000 title claims abstract description 31
- 238000000576 coating method Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 96
- 239000000758 substrate Substances 0.000 claims abstract description 72
- 238000010438 heat treatment Methods 0.000 claims abstract description 60
- 239000007788 liquid Substances 0.000 claims abstract description 43
- 239000000725 suspension Substances 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 229910001297 Zn alloy Inorganic materials 0.000 claims abstract description 17
- 239000012298 atmosphere Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 238000002844 melting Methods 0.000 claims abstract description 5
- 230000008018 melting Effects 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims abstract description 3
- 239000000945 filler Substances 0.000 claims description 24
- 230000008569 process Effects 0.000 claims description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 230000001681 protective effect Effects 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000011230 binding agent Substances 0.000 claims description 11
- 229910001868 water Inorganic materials 0.000 claims description 11
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- 235000002639 sodium chloride Nutrition 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 150000001298 alcohols Chemical class 0.000 claims description 8
- 239000000080 wetting agent Substances 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 230000001680 brushing effect Effects 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 5
- 239000010959 steel Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- -1 halogen salts Chemical class 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 3
- 230000004907 flux Effects 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 238000005554 pickling Methods 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 229910001018 Cast iron Inorganic materials 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000003929 acidic solution Substances 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 238000005422 blasting Methods 0.000 claims description 2
- 150000001639 boron compounds Chemical class 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052756 noble gas Inorganic materials 0.000 claims description 2
- 150000002835 noble gases Chemical class 0.000 claims description 2
- 235000021317 phosphate Nutrition 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 238000005096 rolling process Methods 0.000 claims description 2
- 150000004756 silanes Chemical class 0.000 claims description 2
- 150000004760 silicates Chemical class 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 238000004381 surface treatment Methods 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 238000005246 galvanizing Methods 0.000 description 9
- 239000002318 adhesion promoter Substances 0.000 description 8
- 239000010410 layer Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000005479 sherardizing Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000009736 wetting Methods 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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/18—Solid state diffusion of only metal elements or silicon into metallic material surfaces using liquids, e.g. salt baths, liquid suspensions
-
- 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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/02—Pretreatment of the material to be coated
-
- 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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/18—Solid state diffusion of only metal elements or silicon into metallic material surfaces using liquids, e.g. salt baths, liquid suspensions
- C23C10/20—Solid state diffusion of only metal elements or silicon into metallic material surfaces using liquids, e.g. salt baths, liquid suspensions only one element being diffused
-
- 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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/18—Solid state diffusion of only metal elements or silicon into metallic material surfaces using liquids, e.g. salt baths, liquid suspensions
- C23C10/20—Solid state diffusion of only metal elements or silicon into metallic material surfaces using liquids, e.g. salt baths, liquid suspensions only one element being diffused
- C23C10/24—Salt bath containing the element to be diffused
-
- 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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
-
- 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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
- C23C10/30—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes using a layer of powder or paste on the surface
-
- 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
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
Definitions
- the present invention relates to a method for diffusion coating a surface of a metallic substrate with zinc, wherein the substrate to be coated is heat-treated together with zinc as a diffusion source at a temperature between 200 and 500 ° C, but below the melting temperature of the diffusion source.
- Components made of corrosion-susceptible material such as iron and steel have been galvanized for a long time, i. provided on its surface with a comparatively thin layer of zinc to increase the corrosion resistance of the components.
- Examples of such components are connecting and fastening elements, such as screws and bolts, body parts for motor vehicles, crash barriers, railings, external stairs and the like.
- galvanizing for example, the hot-dip galvanizing, electroplating and Sherardizing are known.
- the substrate to be coated after a corresponding pretreatment, which conventionally comprises the steps degreasing, pickling, fluxing and drying, is immersed in a molten zinc, which usually has a temperature between 440 to 460 ° C., and for a sufficient time in this melt leave before the thus coated substrate removed from the melt, cooled and optionally post-treated.
- a disadvantage of hot-dip galvanizing is found in the attempt to coat coated high-strength steel parts, because under the influence of the relatively high process temperature, these can lose crucial strength and thus become unusable.
- Another known galvanizing is the Sherardisierverfah- ren, in which the galvanizing zinc powder is usually heat treated at a temperature between 320 and 420 0 C in admixture with an inert material or filler, such as sand or ceramic, for example alumina.
- an inert material or filler such as sand or ceramic, for example alumina.
- the method is carried out in a heatable rotating drum, which is also referred to as a retort, in which the galvanizing material is embedded in the mixture of zinc powder and filler, before the drum is sealed airtight after being infested and heated to the required temperature.
- the filler used in the sherardization process has several functions. On the one hand, this ensures uniform heating, gentle cleaning of the components and a homogeneous distribution of the zinc powder.
- the sherardization process is a diffusion coating process in which zinc from the vapor phase, which is formed by sublimation due to the comparatively high vapor pressure of zinc at the temperature used for the heat treatment, diffuses into the surface layer of the substrate to be galvanized.
- Such processes are described for example in DE-PS 134 594, in DE-PS 273 654 and EV Proskurkin & NS Gorbunov, "Galvanizing, sherardizing and other zinc diffusion coatings", Technicopy Limited, England, 1972, pages 1-68. 89
- a disadvantage of the known Sherardisierclar is the comparatively high zinc consumption, which is caused by the combustion of zinc in the initially present in the reaction space air atmosphere with an oxygen concentration of 21 vol .-%, because the burned zinc is no longer available for coating.
- retorts commonly used in the sherardizing process are also disadvantageous.
- retorts are used for this purpose, which are rotated or moved in an oven so as to achieve a uniform distribution of the zinc dust and the filler, and to make the number of ovens lower than that of the Retorts can be kept.
- the seals are also within the combustion chamber. Since these are not completely tight, air and gaseous oxygen-containing combustion products can enter the retort during the heat treatment, which impairs the process reliability and, in particular, increases the zinc consumption for the above reasons.
- the object of the present invention is therefore to provide a method for diffusion coating a surface of a substrate with zinc, which can be used to obtain very uniform zinc coatings with excellent corrosion resistance, even when complicatedly formed substrates are used a rotating or otherwise moving retort must be performed, which, based on the surface of the to zinciferous substrate, low zinc consumption and can be dispensed with the use of filler and the use of loose zinc dust during the heat treatment.
- this object is achieved by providing a method according to claim 1 and in particular a method for diffusion-coating a surface of a metallic substrate with zinc, which comprises the following steps:
- step b) drying the substrate obtained in process step a ⁇ or a2), c) carrying out a heat treatment of the substrate obtained in process step b) at a temperature between 200 and 500 ° C, but preferably below the melting temperature of the diffusion source under a protective gas atmosphere forming a zinc-containing diffusion layer on the substrate, and d) removing the mixture applied in step a ⁇ or aa).
- the reaction chambers used in the process according to the invention unlike the Sherardisier processor usually used in ovens positioned movable retorts can be made much simpler, which reduces investment costs.
- the substrates to be coated in the reaction space do not have to be stored on a rack, in contrast to the movable retorts conventionally used in sherardization processes.
- the zinc consumption is further reduced in the inventive method, because it is possible due to the application of the zinc as a firmly adhering layer on the substrate surface to be coated before performing the heat treatment, only as much zinc on the substrate surface, as for the later Coating is required. For this reason, the zinc used in the process according to the invention is at least almost completely consumed. For this reason too, the process costs in the process according to the invention are significantly lower than in the processes known from the prior art.
- a protective gas atmosphere is understood as meaning a gas or gas mixture which is less than 10%, preferably less than 1%, more preferably less than 100 ppm, even more preferably less than 10 ppm, very preferably less than 1 ppm and most preferably contains at most 0, 1 ppm oxygen.
- the application of the diffusion source zinc according to the process step ai), ie it is applied to the surface to be coated of the substrate, a suspension containing a liquid and zinc and / or a zinc alloy.
- the liquid used is preferably water, and more preferably distilled water. Since liquids containing water or water react or react with zinc with hydrogen formation at elevated temperatures, a cooled suspension is preferably used in process step a 1, more preferably one at a temperature of less than 20 ° C., and most preferably cooled to a temperature of less than 10 0 C suspension.
- liquid hydrocarbons As an alternative to water, it is also possible to use liquid hydrocarbons, alcohols or ketones or other liquids or liquid mixtures as liquid, provided that they are volatile, if necessary react to a limited extent with zinc and preferably dissolve salts.
- Preferred examples of these are trichlorethylene, dichloromethane, benzene, xylene, toluene or C 1 -C 10 alcohols, in particular methanol, ethanol, propanol and butanol.
- the suspension used in process step a ⁇ may be added to at least one further compound, which is selected from the group, in addition to the liquid and the zinc or zinc alloy which consists of dispersants, binders, wetting agents and any mixtures of two or more of the aforementioned compounds. While the dispersant improves the homogeneity of the suspension, and thus uniform application of the diffusion source to the substrate surface, and the wetting agent facilitates wetting of the substrate surface, the binder acts as an adhesion enhancing adhesive.
- the application of the diffusion source zinc is carried out according to method step a2), ie first a liquid, preferably an adhesion promoter, is applied to the surface of the substrate to be coated before subsequently applying to the liquid or liquid Adhesive zinc and / or a zinc alloy is applied.
- a liquid preferably an adhesion promoter
- Adhesive zinc and / or a zinc alloy is applied.
- a solvent is optionally used in admixture with at least one further compound selected from the group consisting of dispersants, binders, wetting agents and any mixtures of two or more of the aforementioned compounds.
- the solvent used is preferably water, and more preferably distilled water.
- Water can also be used as solvent liquid hydrocarbons, alcohols or ketones or other liquids or liquid mixtures, provided that they are volatile, if necessary, react with limited zinc and preferably salts can solve.
- Preferred examples of these are trichlorethylene, dichloromethane, benzene, xylene, toluene or C 1 -C 1 0 alcohols, in particular methanol, ethanol, propanol and butanol.
- good adhesion of the zinc or zinc alloy to the substrate surface to be coated is achieved by drying the liquid applied to the substrate surface or the adhesive applied to the substrate surface in process step b) Zinc reached.
- at least one compound selected from the group consisting of dispersant, binder, and the liquid / adhesion promoter used in process step a2) may be added. Wetting agent and any mixtures of two or more of the aforementioned compounds.
- the suspension applied in method step a 1 or the liquid / adhesion promoter applied in method step a 2) at least one binder, wherein the binder is preferably selected from the group consisting of halogen salts, sulfates, sulfites, phosphates, silicates, boron compounds, water glass and any mixtures of two or more of the aforementioned compounds.
- the binder is selected from zinc chloride, sodium chloride, potassium chloride, ammonium chloride, zinc sulfate and any mixtures of two or more of the aforementioned compounds.
- the suspension or the liquid / adhesion promoter applied in process step a) may preferably contain at least one compound which is selected from the group consisting of surfactants and alcohols.
- suitable alcohols are methanol, ethanol, propanol, butanol or pentanol.
- the applied suspension or applied in the step a2), liquid prior to application to the substrate to a temperature of less than 20 ° C and cooled in step ai) preferably to a temperature of less than 10 0 C.
- An exemplary suspension suitable for carrying out the first embodiment of the present invention may be, for example, water saturated with sodium chloride, zinc, zinc chloride (for example, in an amount of 1% by weight) and alcohol (preferably ethanol or methanol).
- An example of a suitable adhesion promoter for carrying out the second embodiment of the present invention is, for example, a solution consisting of water, sodium chloride, zinc chloride and alcohol (preferably ethanol or methanol).
- zinc in the form of zinc powder or zinc dust having an average particle size of not more than 100 ⁇ m, preferably not more than 20 ⁇ m and particularly preferably not more than 10 ⁇ m, is used in method step ai) or alternatively in method step a2).
- zinc powder or zinc dust having an average particle size of not more than 100 ⁇ m, preferably not more than 20 ⁇ m and particularly preferably not more than 10 ⁇ m is used in method step ai) or alternatively in method step a2).
- zinc powder or zinc dust having an average particle size of not more than 100 ⁇ m, preferably not more than 20 ⁇ m and particularly preferably not more than 10 ⁇ m
- Zinc dust with a mean particle size between 3 and 6 ⁇ m and with a maximum particle size of 70 ⁇ m will get good results.
- the zinc used has a zinc content between 90 and 100 wt .-% and particularly preferably a zinc content between 99 and 100 wt .-%.
- the present invention is not limited. This can be done for example by spraying, dipping, brushing, rolling or brushing.
- the diffusion medium ie the zinc or the zinc alloy
- the drying in the process step b) is carried out at a temperature between 40 and 250 0 C.
- the substrate may additionally lent before coating, ie before step c) and preferably before Step b), preferably to a temperature between 40 and 250 0 C are heated.
- the heat treatment in process step c) can in principle be carried out at any temperature and duration known for conventional sherardization processes.
- the heat treatment is carried out at a temperature between 300 and 420 0 C and particularly preferably at a temperature between 340 and 410 0 C.
- the heat treatment should preferably be carried out at a temperature lower than the melting temperature of the diffusion source, ie, the zinc or the zinc alloy applied in the step ai) and / or Si2), otherwise there is a fear of sintering of the substrate surface ,
- the duration of the heat treatment may be, for example, between 10 minutes and 10 hours.
- the heat treatment according to the invention is carried out under a protective gas atmosphere
- protective gas atmosphere here is a gas or a gas mixture is called which contains less than 10% oxygen.
- Particularly good results are obtained when the protective gas atmosphere during the heat treatment in process step c) less than 1%, more preferably less than 100 ppm, even more preferably less than 10 ppm, most preferably less than 1 ppm and most preferably not more than 0 Contains 1 ppm oxygen.
- the present invention is not limited in the pressure at which the heat treatment is performed.
- the heat treatment can be carried out at atmospheric pressure or a slight overpressure of up to 1.5 bar, preferably between 1.02 and 1.2 bar. This ensures that in the event of accidental leakage in the retort during the heat treatment, no air enters the retort.
- the process according to the invention is preferably carried out without filler.
- the filler content in the retort during the heat treatment is less than 20%, more preferably less than 10% and most preferably less than 1% ,
- the retort with the substrate to be coated and the diffusion source adhered thereto is first heated to the heat treatment temperature before the temperature is maintained for a time sufficient for the heat treatment and the retort is finally cooled to room temperature.
- heat treatment is understood to be the period of time during which the temperature required for heat treatment is maintained, ie excludes during the heating and cooling phase.
- the heat treatment is carried out under a protective gas atmosphere, whereas during the heating rate and / or the cooling phase no Intergasatmo- sphere must be present, although this is less preferred.
- the oxygen content in the atmosphere contained in the reaction space in which the heat treatment is carried out already before the start of the heat treatment i. before the temperature at which the heat treatment is carried out, ie already before or at the latest during the heating phase, to less than 10%, preferably less than 1%, more preferably less than 100 ppm, even more preferably less than 10 ppm, more preferably less than 1 ppm and most preferably not more than 0.1 ppm. This reliably prevents zinc from being burnt when the reaction chamber is heated up by oxygen.
- the reaction space in which the process step c) is carried out to reduce the oxygen content in the protective gas atmosphere contained in the reaction space to less than 10%, preferably to less than 1%. , more preferably less than 100 ppm, even more preferably less than 10 ppm, most preferably less than 1 ppm, and most preferably not more than 0.1 ppm oxygen to be adjusted or maintained until the temperature in the reaction space after completion of the heat treatment is cooled to less than 200 0 C / has been.
- the mixture or the diffusion source applied after the heat treatment is removed from the coated substrate by, for example, washing, ultrasonic treatment or brushing of the coated substrate in the process step a or the process step.
- the coated substrate can be passivated after the heat treatment, preferably after removal of the mixture applied in process step ai) or in process step a2).
- the method according to the invention is particularly suitable for coating substrates which consist of a zinc-settable metal, preferably iron and its alloys, such as steel and cast iron, copper and its alloys and / or aluminum and its alloys.
- a zinc-settable metal preferably iron and its alloys, such as steel and cast iron, copper and its alloys and / or aluminum and its alloys.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
L'invention concerne un procédé de revêtement de diffusion d'une surface d'un substrat métallique avec du zinc comprenant les étapes consistant à : a1) appliquer une suspension, comprenant un liquide et du zinc et/ou un alliage de zinc utilisé en tant que source de diffusion ou donneur de zinc, à la surface du substrat à recouvrir, ou a2) appliquer un liquide à la surface du substrat à recouvrir et appliquer ultérieurement le zinc et/ou l'alliage de zinc utilisé en tant que source de diffusion ou donneur de zinc au liquide; et b) sécher le substrat obtenu dans l'étape a1) ou a2); réaliser une traitement thermique du substrat obtenu dans l'étape b) à une température comprise entre 200 et 500°C, mais inférieure à la température de fusion de la source de diffusion dans une atmosphère de gaz de protection; et d) élimination du mélange appliqué dans l'étape a1) et a2).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102009006190A DE102009006190A1 (de) | 2009-01-27 | 2009-01-27 | Zinkdiffusionsbeschichtungsverfahren |
| PCT/EP2010/000489 WO2010086151A1 (fr) | 2009-01-27 | 2010-01-27 | Procédé de revêtement de diffusion de zinc |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP2391742A1 true EP2391742A1 (fr) | 2011-12-07 |
Family
ID=42270275
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP10702601A Withdrawn EP2391742A1 (fr) | 2009-01-27 | 2010-01-27 | Procédé de revêtement de diffusion de zinc |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20120006450A1 (fr) |
| EP (1) | EP2391742A1 (fr) |
| DE (1) | DE102009006190A1 (fr) |
| SG (1) | SG173143A1 (fr) |
| WO (1) | WO2010086151A1 (fr) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2931938B1 (fr) * | 2012-12-12 | 2018-07-18 | Kwik-Coat (Aust) Pty Ltd | Procédé de fabrication de pièces de travail revêtues d'alliage |
| DE102013107011A1 (de) | 2013-07-03 | 2015-01-08 | Thyssenkrupp Steel Europe Ag | Verfahren zum Beschichten von Cu-Langprodukten mit einer metallischen Schutzschicht und mit einer metallischen Schutzschicht versehenes Cu-Langprodukt |
| RU2547057C1 (ru) * | 2013-12-24 | 2015-04-10 | Виктор Иванович Кубанцев | Способ получения защитных покрытий |
| JP6329924B2 (ja) * | 2015-06-19 | 2018-05-23 | 三菱アルミニウム株式会社 | 熱交換器用アルミニウム合金管および熱交換器コア |
| CN105648399B (zh) * | 2016-03-24 | 2018-10-26 | 华北电力大学(保定) | 一种碳钢的表面改性方法 |
| US20180370830A1 (en) * | 2017-06-22 | 2018-12-27 | Purpose Energy, Inc. | System and method for continuous processing of organic waste with undigested solids recirculation |
| EP3425083A1 (fr) * | 2017-07-03 | 2019-01-09 | Ebbinghaus Verbund Management- und Dienstleistungs GmbH | Procédé amélioré et appareil de galvanisation par diffusion à chaud et article ainsi fabriqué |
| DE102017215676A1 (de) * | 2017-09-06 | 2019-03-07 | Bayerische Motoren Werke Aktiengesellschaft | Beschichtungsverfahren |
| NL2023379B1 (en) | 2019-06-25 | 2021-02-01 | Sherart B V | A process for coating a surface of a substrate with a metal layer |
| CN113685470A (zh) * | 2021-08-23 | 2021-11-23 | 南京科赫科技有限公司 | 一种高效防腐蚀碟簧及其加工工艺 |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE134594C (fr) | ||||
| DE273654C (fr) | ||||
| FR645990A (fr) * | 1926-12-23 | 1928-11-06 | Thomson Houston Comp Francaise | Perfectionnement aux procédés de protection des articles métalliques contre la corrosion |
| US1815638A (en) * | 1929-05-24 | 1931-07-21 | Copper Plate Sheet & Tube Comp | Process of plating metal |
| GB1071624A (en) * | 1964-04-14 | 1967-06-07 | Imp Smelting Corp Ltd | Improvements in or relating to the coating of metal surfaces |
| FR2401233A1 (fr) * | 1977-08-22 | 1979-03-23 | Anvar | Procede de traitement superficiel de l'acier par le zinc |
| US4391855A (en) * | 1980-08-25 | 1983-07-05 | Depor Industries | Corrosion resistant coating and method for coating metal substrate |
| US4542048A (en) * | 1983-07-07 | 1985-09-17 | Inland Steel Company | Powder metal and/or refractory coated ferrous metals |
| US4628004A (en) * | 1983-07-07 | 1986-12-09 | Inland Steel Company | Powder metal and/or refractory coated ferrous metal |
| JPS60200975A (ja) * | 1984-03-23 | 1985-10-11 | Hitachi Cable Ltd | 金属管材の内面処理方法 |
| JPH0192355A (ja) * | 1987-09-30 | 1989-04-11 | Hitachi Cable Ltd | 亜鉛合金被覆鋼線およびその製造方法 |
| FR2701719B1 (fr) * | 1993-02-19 | 1995-04-14 | Maubeuge Fer | Procédés et installations pour réaliser en continu plusieurs revêtements à base d'alliage métallique sur une bande d'acier. |
| DE102008020576B4 (de) * | 2008-04-24 | 2018-06-28 | Bodycote Wärmebehandlung GmbH | Verfahren zum Diffusionsverzinken |
-
2009
- 2009-01-27 DE DE102009006190A patent/DE102009006190A1/de not_active Withdrawn
-
2010
- 2010-01-27 EP EP10702601A patent/EP2391742A1/fr not_active Withdrawn
- 2010-01-27 SG SG2011053956A patent/SG173143A1/en unknown
- 2010-01-27 WO PCT/EP2010/000489 patent/WO2010086151A1/fr not_active Ceased
- 2010-01-27 US US13/146,316 patent/US20120006450A1/en not_active Abandoned
Non-Patent Citations (1)
| Title |
|---|
| See references of WO2010086151A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| US20120006450A1 (en) | 2012-01-12 |
| DE102009006190A1 (de) | 2010-07-29 |
| WO2010086151A8 (fr) | 2010-11-11 |
| SG173143A1 (en) | 2011-08-29 |
| WO2010086151A1 (fr) | 2010-08-05 |
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