WO1992006231A2 - Procede et dispositif de decapage, ainsi que procede et installation de galvanisation - Google Patents
Procede et dispositif de decapage, ainsi que procede et installation de galvanisation Download PDFInfo
- Publication number
- WO1992006231A2 WO1992006231A2 PCT/BE1991/000071 BE9100071W WO9206231A2 WO 1992006231 A2 WO1992006231 A2 WO 1992006231A2 BE 9100071 W BE9100071 W BE 9100071W WO 9206231 A2 WO9206231 A2 WO 9206231A2
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- WO
- WIPO (PCT)
- Prior art keywords
- elements
- bath
- pickling
- baths
- electrode
- Prior art date
Links
- 238000005554 pickling Methods 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 48
- 238000005246 galvanizing Methods 0.000 title claims description 22
- 238000009434 installation Methods 0.000 title claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 55
- 238000005238 degreasing Methods 0.000 claims abstract description 24
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000460 chlorine Substances 0.000 claims abstract description 23
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 23
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 13
- 239000011707 mineral Substances 0.000 claims abstract description 13
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 12
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000010959 steel Substances 0.000 claims abstract description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 27
- 229910052725 zinc Inorganic materials 0.000 claims description 27
- 239000011701 zinc Substances 0.000 claims description 27
- 230000008569 process Effects 0.000 claims description 22
- 150000003839 salts Chemical class 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 4
- 238000011144 upstream manufacturing Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001804 chlorine Chemical class 0.000 claims description 2
- 238000010924 continuous production Methods 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 238000005530 etching Methods 0.000 claims 4
- 238000001035 drying Methods 0.000 claims 1
- 239000002184 metal Substances 0.000 abstract 1
- 239000012266 salt solution Substances 0.000 abstract 1
- 239000000314 lubricant Substances 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 235000010755 mineral Nutrition 0.000 description 9
- 238000004381 surface treatment Methods 0.000 description 8
- 238000007664 blowing Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- 238000005491 wire drawing Methods 0.000 description 4
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000012777 electrically insulating material Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical class [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
-
- 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
- C23C2/003—Apparatus
- C23C2/0038—Apparatus characterised by the pre-treatment chambers located immediately upstream of the bath or occurring locally before the dipping process
-
- 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
- C23C2/003—Apparatus
- C23C2/0038—Apparatus characterised by the pre-treatment chambers located immediately upstream of the bath or occurring locally before the dipping process
- C23C2/004—Snouts
-
- 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
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
-
- 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
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/024—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by cleaning or etching
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F7/00—Constructional parts, or assemblies thereof, of cells for electrolytic removal of material from objects; Servicing or operating
Definitions
- the present invention relates to a process of pickling, and optionally degreasing, of long metallic elements, in particular steel wires, strips and profiles, according to which these elements are introduced into an electrolyte solution in which a electric current through electrodes.
- a process as defined above is known in particular from European patent 0209.618.
- One of the essential aims of the present invention is, on the one hand, to remedy the drawbacks of the process which is the subject of European patent n ° 0209.618, in particular the need to use a frequency converter, and, on the other hand, to propose a process which may be suitable for any type of electric current, both direct current and alternating current at the frequency of the electricity distribution network.
- these elements are moved, preferably in a substantially continuous manner, in the direction of their length through at least two successive separate baths containing an aqueous solution of hydrochloric acid and / or of a chlorine mineral salt in each of which is placed at least one electrode, an electric voltage being applied to these electrodes in such a way that the sign of the voltage at the electrode of one of the baths is always different from the sign of the voltage at the electrode of the neighboring bath, the baths being isolated from each other so that the electric current passes between two neighboring baths essentially via the part of the element moving between these two neighboring baths.
- the invention also relates to a device for implementing this method.
- This device is characterized by the fact that it comprises at least two successive baths each intended to contain a solution of hydrochloric acid and / or a chlorine mineral salt, electrically isolated from one another, at through which the long metallic elements move, an electrode being placed in each of these baths at a certain distance, preferably below, from the place of passage of the abovementioned elements, the electrode of a determined bath being connected to a poles of a low voltage electric current generator, the electrode of an adjacent bath being connected to the other pole of this generator.
- the invention also relates to a continuous process for galvanizing long elements, in particular steel wires, strips and profiles, comprising at least one heat treatment step, a pickling step possibly combined with a degreasing and a covering step. of the surface of these elements of a zinc-based film, these elements being moved in a substantially continuous manner in the direction of their length through these stages, pickling comprising passing the elements through a bath of an electrolyte solution, in particular of a mineral acid.
- the wires to be galvanized generally have a surface covered with two distinct substances, namely i 1) of the oxide of the base metal, 2) a drawing lubricant, such as stearates, phosphates, etc.
- these two substances must be eliminated while limiting the loss of base metal to the strict minimum.
- the surface treatment precedes the heat treatment.
- these methods have the drawback of not being able to reach high galvanization rates, the difficulty being the duration of the reduction of the oxide during the heat treatment.
- chemical surface treatment with acid is excluded since the drawing lubricant is not soluble in acid. The surface treatment thus takes place electrolytically, using direct current.
- the heat treatment takes place before the surface treatment.
- the wire drawing lubricant on the surface of the wire is either
- the surface treatment is chemical pickling with hydrochloric acid; at ambient temperature of the acid (25 ° C), the pickling time is approximately 15 seconds; this time can be reduced to about 8 seconds by raising the acid temperature to 60 ° C, but the acid vapors released then make the operating conditions difficult.
- Electrolytic processes (HriftSO. In DC current for example) are hardly ever used. Indeed, the pickling time is also long, of the order of 10 seconds. In addition, sulfates are difficult to remove when rinsing with water, even -r -
- One of the essential aims of the present invention is to present a new galvanizing process, which makes it possible to remedy the drawbacks of known galvanizing processes, in particular by the use of a pickling step, possibly combined with a very effective simultaneous degreasing which will result in a significant reduction not only of the total time of galvanization but also of the equipment of the installation itself of galvanization, more particularly by the elimination of a step of fluxing separated from the zinc bath which is essential in the traditional processes galvanizing.
- a bath of an aqueous hydrochloric acid solution and / or a mineral salt of chlorine is used in the pickling step, in which an electric current is created. in such a way that this current passes through these elements during their passage through the above-mentioned bath.
- the invention also relates to a galvanizing installation for the implementation of the new process mentioned above.
- This installation includes an oven for heat treatment, a pickling and optionally degreasing device, and a bath of molten zinc or electrolytic zinc.
- Figure 1 is a schematic longitu ⁇ dinal representation of a galvanizing line according to a first particular embodiment of the invention.
- Figure 2 is a representation similar to that of Figure 1 of a second particular embodiment of a galvanizing line according to the invention.
- Figure 3 is a schematic representation, on a larger scale, of an essential part of a pickling device according to an advantageous embodiment of the invention.
- the figure is a partial perspective view, on a larger scale, of a tank of a pickling device according to a particular embodiment of the invention.
- the invention is not necessarily limited to a process and an installation for galvanizing, but in fact relates, in general, to a process and a device for pickling and possibly degreasing which can be applied in any industrial area where pickling with possible degreasing is necessary.
- galvanizing is a preferred application given the very significant technical advantages obtained in this specific application. For this reason, the description given below will essentially relate to a process and a galvanizing installation in which the particular pickling process and device, according to the invention, are implemented.
- Figure 1 schematically shows a continuous galvanizing installation comprising, in addition to drive means known per se for moving steel wires 10 continuously and in the direction of their length through this installation, a degreasing and pickling device 1 for these steel wires 10, an oven 18 for the heat treatment of the wires and a tank 20 containing molten zinc to cover the pickled and degreased wires with a film of zinc.
- the aforementioned pickling device 1 comprises, in the particular embodiment shown in FIG. 1, four successive tanks 2, 3, and 5, the walls of which are made of a material which does not conduct electric current, such as polyvinyl chloride. or polyethylene and which are mounted at a certain distance from each other in a collecting tank 6.
- Passage openings 7 for the wires 10 are provided both in opposite walls of the collecting tank
- the electrode 8 of a given tank is connected to one of the poles of a low voltage electric current generator, the electrode of an adjacent tank being connected to the other pole of this generator.
- the electrode of the first tank 2 is at a positive potential
- the electrode of tank 3 will be at a negative potential
- the electric current generator itself has not been shown but simply conductors 9 on which the electrodes 8 of the different tanks are connected in parallel.
- the electric current generator can be a direct current or alternating current generator.
- this generator is advantageously formed by the electrical current distribution network, the frequency of which is for example 50 or 60 Hertz, depending on the country where the installation is installed.
- Each of the tanks contains a solution of hydrochloric acid or a chlorine mineral salt, the level of which is above the passage openings 7 for the wires 10. In this way, the wires 10, passing through these openings 7 to through tanks 2 to 5, will be immersed in the hydrochloric acid solution and / or a mineral salt of chlorine.
- the solution of hydrochloric acid and / or an inorganic salt of chlorine contained in the tanks 2 to 5 is continuously poured through the passage openings 7 into the collecting tank 6.
- the solution recovered in the collecting tank 6 is recirculated by a pump 13 and a supply conduit 14 * to the tanks 2 to 5.
- This conduit 1 preferably opens into one of the side walls of each of these tanks at or slightly below the level passage of the wires 10 in these tanks, so as to create a current of the electrolyte solution transversely to the direction of displacement of the wires 10 (see FIG. 4).
- the collecting tank 6 containing the various tanks 2 to 5 is preferably mounted below a suction hood 15, which allows the evacuation of the gases formed and any vapors of the electrolyte.
- the pickled and degreased wires leaving the device 1 immediately enter an air blowing box 16 to allow the acid entrainments to be forced upstream on the surface of the wires 10. Then the wires pass through a unit of rinsing with water 17.
- a second air blowing box 16 'mounted downstream of the rinsing unit 17 eliminates the entrainment of water on the wires.
- This oven is extended by a sealed chamber 19 which opens into a molten zinc tank 20.
- the sealed chamber 19 is for example formed by tubes extending in the extension of the tubes of the furnace 18 and ending in a box 19 'open downward and partially dipping into the molten zinc tank 20.
- This chamber 19 as well as the oven 18 are supplied with neutral or slightly reducing gas, for example nitrogen containing a small amount of hydrogen.
- This gas is for example supplied by a cylinder 21 and circulates against the current of the wires up to the outlet of the oven 18 to escape into the open air, thus ensuring the protection of the wires against oxidation for the duration of the heat treatment.
- the wires 10 having undergone the heat treatment in the furnace 18 are deflected downwards into the tubes of the chamber 19 in order then to be immersed immediately, at the location of the box 19 ′, in the molten zinc contained in the tank 20 for undergo a coating of zinc film there.
- the wires then leaving the molten zinc bath undergo wiping according to known techniques, so that such a wiping unit has not been shown in FIG. 1.
- FIG. 2 relates to a second embodiment of a galvanizing installation according to the invention which differs essentially from the first embodiment represented in FIG. 1 by the fact that the heat treatment takes place upstream of the pickling.
- a great advantage of this second embodiment is that in principle any type of oven can be used to carry out this heat treatment, unlike what is the case in the first embodiment where significant precautions must be taken to avoid reoxidation of the surface of the wires during this heat treatment.
- a fluidized bed oven 18 is advantageously used, so as to obtain an efficient heat exchange with the wires which pass through it.
- the wires leaving the oven 18 will immediately enter a cooling unit 22, so as to minimize the oxidation of the surface of the wires.
- the wires 10 enter the pickling device 1 which is similar to that of the first embodiment. If necessary, the number of tanks crossed by the wires could be different as a result of the fact that the wires are generally covered by a crust of burnt lubricant and that degreasing is in fact no longer necessary. Also, as in the first embodiment, the pickling device is successively followed by a blowing box 16, a rinsing unit 17 and a second blowing box 16 '.
- the wires dried in the second blowing box 16 ′ then enter the sealed chamber 19.
- a flux could be provided on the surface of the molten zinc bath, inside the box 19 ′, which would for example be formed by a layer 25 of a double salt of zinc chloride and floating ammonium on the surface of the molten zinc bath and through which the wires 10 penetrate before entering the molten zinc 20.
- This double salt is supplied from a tank 26.
- the electrodes 8 are preferably made of graphite.
- the voltage applied to the electrodes 8 is advantageously a uniform direct voltage or not, for example a pulsed current, or an alternating voltage.
- the frequency of this voltage advantageously corresponds to that of the electric current distribution network of the region where the installation is mounted. It is generally a frequency of 50 or 60 Hertz. In this case, it is sufficient to insert a transformer between the electrical current distribution network and the electrodes if one wishes to change the intensity of the current and the voltage at the electrodes.
- the density of the electric current in the bath the solution of hydrochloric acid and / or an inorganic salt of chlorine is advantageously between 10 and 600 A / dm 2 , preferably between 50 and 500 A / dm 2 .
- the concentration of hydrochloric acid in the bath is between 100 and 300 g / l and preferably between 120 and 250 g / l
- the temperature of the bath can generally vary between 15 and 70 ° C, preferably between 20 and 60 ° C.
- the number and the size of the different tanks and the electrodes are chosen as well as the distance of the latter with respect to the wires, as well as the working parameters so that the time of pickling or stay of the wires in the different baths is a total of 1 to 5 sec.
- the electrode of a neighboring cell When a determined electrode is at a positive voltage, the electrode of a neighboring cell is at a negative voltage. The portions of wires located opposite the positive electrode are negatively charged, while the portions of wires in the adjacent tank opposite the negative electrode are charged positively.
- This pickling and degreasing operation is advantageously improved by subjecting the wires to a vibration so as to favor the action of the bubbles and their continuous and rapid detachment from the surface of the wires.
- Native chlorine on the surface of the positively charged wire portions is very active and therefore strongly attacks the surface of these wire portions.
- hydrochloric acid gas formed near the surface of the wires as mentioned above, being very soluble in water, will therefore go into solution in the bath. Part of the hydrogen formed will be released from the bath and a corresponding part of chlorine will react with water to reform hydrochloric acid with production of oxygen, the latter therefore also being released from the bath.
- FIG. 3 relates to a variant of certain constructive parts of the pickling device, according to the invention, which can be used in the galvanizing installations illustrated diagrammatically by FIGS. 1 and 2.
- electrodes 8 the face of which faces towards the wires 10 is curved so that the distance between the electrode and the wires moving opposite the latter, gradually increases as the wires move on either side of the middle of this electrode towards its two edges extending transversely to this direction of movement.
- the collecting tank 6 can be divided into compartments by a partition 11 also made of an electrically insulating material. Each tank through which the wires to be stripped and degreased are then found in a separate compartment.
- a separate recirculation system comprising a pump 13 and a supply line 14, is then provided for each group of compartment and tank.
- Such a construction of the galvanizing and pickling device allows a more flexible adjustment of the pickling baths in each of the tanks. If necessary, the concentration of hydrochloric acid can be varied from one tank to another.
- openings 23 can be provided in the boxes 11, preferably near the bottom of the tank 6, allowing the electrolyte solution to pass from one compartment to the other.
- valves could be provided to adjust the section of these openings 23 and even to close them when deemed necessary. It is preferably necessary to avoid that the jets 24 of the solution overflowing from neighboring tanks can touch each other to prevent a passage of electric current from one tank to another by these jets.
- Electrolyte temperature 20 ° C - Wire running speed: variable, greater than 100 m / min.
- Thread speed 70 m / min.
- Number of electrodes 10. Intensity 15A
- the electrolyte was formed from an aqueous solution of 5% NaCl.
- the invention is not limited to the embodiments described above and that many variants could be envisaged without departing from the scope of the present invention.
- the wires passing through the various successive baths can be guided on the edges of the tanks over which the acid solution overflows with a continuously with a sufficiently large flow so that the wires are completely immersed in the overflowing solution.
- electrodes could also be provided above the wires.
- alternating current could be superimposed on direct current.
- the zinc film on the surface of the long members 10 can be formed by electrolysis.
- the electrolyte solution is formed from hydrochloric acid and at the same time from an inorganic salt of chlorine, both the acid and this salt will be in a dissociated form, as will be the case. if the solution is formed only from hydrochloric acid or a mineral salt of chlorine.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP91916209A EP0560771A1 (fr) | 1990-10-08 | 1991-10-04 | Procede et dispositif de decapage, ainsi que procede et installation de galvanisation |
US08/039,084 US5449447A (en) | 1990-10-08 | 1991-10-04 | Method and device for pickling and galvanizing |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BE9000950A BE1005217A3 (fr) | 1990-10-08 | 1990-10-08 | Procede et dispositif de degraissage et de decapage de fils ou rubans metalliques ou d'elements analogues. |
BE9000950 | 1990-10-08 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO1992006231A2 true WO1992006231A2 (fr) | 1992-04-16 |
WO1992006231A3 WO1992006231A3 (fr) | 1992-11-26 |
Family
ID=3884959
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/BE1991/000071 WO1992006231A2 (fr) | 1990-10-08 | 1991-10-04 | Procede et dispositif de decapage, ainsi que procede et installation de galvanisation |
Country Status (4)
Country | Link |
---|---|
US (1) | US5449447A (fr) |
EP (1) | EP0560771A1 (fr) |
BE (1) | BE1005217A3 (fr) |
WO (1) | WO1992006231A2 (fr) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0644276A1 (fr) * | 1993-09-17 | 1995-03-22 | Hitachi, Ltd. | Procédé et dispositif pour la fabrication et le décapage de tôles d'acier laminées à chaud |
US5449447A (en) * | 1990-10-08 | 1995-09-12 | Le Four Industriel Belge S.A. | Method and device for pickling and galvanizing |
EP0695818A1 (fr) * | 1994-07-07 | 1996-02-07 | MANNESMANN Aktiengesellschaft | Procédé et dispositif pour traitement de surface électrolytique |
CN108624939A (zh) * | 2017-03-21 | 2018-10-09 | 宜兴北宸科技有限公司 | 节能环保垂直镀阶梯式连续电镀生产系统 |
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US6276072B1 (en) * | 1997-07-10 | 2001-08-21 | Applied Materials, Inc. | Method and apparatus for heating and cooling substrates |
US6994776B2 (en) * | 1998-06-01 | 2006-02-07 | Semitool Inc. | Method and apparatus for low temperature annealing of metallization micro-structure in the production of a microelectronic device |
US6136163A (en) * | 1999-03-05 | 2000-10-24 | Applied Materials, Inc. | Apparatus for electro-chemical deposition with thermal anneal chamber |
US7192494B2 (en) * | 1999-03-05 | 2007-03-20 | Applied Materials, Inc. | Method and apparatus for annealing copper films |
US20040079633A1 (en) * | 2000-07-05 | 2004-04-29 | Applied Materials, Inc. | Apparatus for electro chemical deposition of copper metallization with the capability of in-situ thermal annealing |
US7311810B2 (en) * | 2003-04-18 | 2007-12-25 | Applied Materials, Inc. | Two position anneal chamber |
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CN102758236A (zh) * | 2012-06-29 | 2012-10-31 | 江苏晨力实业有限公司 | 不锈钢板、带材连续着色设备 |
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ITUB20153726A1 (it) * | 2015-09-18 | 2017-03-18 | Extra Brushes S R L | Procedimento per la realizzazione di una spazzola industriale o per hobbistica e spazzola cosi ottenuta. |
CN106269987A (zh) * | 2016-08-24 | 2017-01-04 | 江苏星火特钢有限公司 | 一种钢丝拉拔前去油处理工艺和系统 |
Citations (5)
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US2860092A (en) * | 1957-12-31 | 1958-11-11 | American Can Co | Electropickling process |
FR1488623A (fr) * | 1965-06-30 | 1967-07-13 | Bekaert Pvba Leon | Procédé et installation de revêtement d'acier |
AU4499468A (en) * | 1969-09-22 | 1971-03-25 | Australian Iron & Steel Pty. Limited | Improvements insteel strip pickling |
EP0202870A1 (fr) * | 1985-05-17 | 1986-11-26 | David Reznik | Appareil et procédé pour traitement anodique |
EP0209168A1 (fr) * | 1985-07-12 | 1987-01-21 | N.V. Bekaert S.A. | Procédé et dispositif pour le nettoyage par décapage électrochimique en utilisant un courant alternatif d'une fréquence spécifiée |
Family Cites Families (12)
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US2372599A (en) * | 1940-03-29 | 1945-03-27 | John S Nachtman | Electrolytic cleaning and pickling of metal surfaces |
US2719820A (en) * | 1951-01-26 | 1955-10-04 | United States Steel Corp | Method for coating steel strip |
US3338809A (en) * | 1966-06-23 | 1967-08-29 | United States Steel Corp | Method of cleaning ferrous metal strands electrolytically, including moving said strands in a horizontal plane through an electrolyte while under the influence of alternating electrical fields |
JPS5017420B1 (fr) * | 1970-08-19 | 1975-06-20 | ||
US3914481A (en) * | 1973-03-01 | 1975-10-21 | Theodore Bostroem | Process of hot dip metallizing of metallic articles |
GB1465431A (en) * | 1976-01-09 | 1977-02-23 | Electricity Council | Electrolytic treatment of elongate articles such as bars tubes or strips |
JPS5347336A (en) * | 1976-10-12 | 1978-04-27 | Kogyo Gijutsuin | Method descaling band steel by electrolysis |
PL124218B1 (en) * | 1979-04-26 | 1983-01-31 | Produkcji Montazu Obiek K | Process for wasteless metallizing,especially zinc coating of steel surface |
ATE15236T1 (de) * | 1981-02-18 | 1985-09-15 | Mannesmann Ag | Vorrichtung zur chemischen oder elektrochemischen oberflaechenbehandlung von behandlungsgut in einem erwaermten fluessigen behandlungsmedium, insbesondere bandbeizanlage. |
JPH01136999A (ja) * | 1987-11-20 | 1989-05-30 | Kobe Steel Ltd | 線条材の電解処理方法 |
US5069158A (en) * | 1990-03-27 | 1991-12-03 | Italimpianti Of America, Inc. | Hydrostatic bearing support of strip |
BE1005217A3 (fr) * | 1990-10-08 | 1993-06-01 | Four Industriel Belge | Procede et dispositif de degraissage et de decapage de fils ou rubans metalliques ou d'elements analogues. |
-
1990
- 1990-10-08 BE BE9000950A patent/BE1005217A3/fr not_active IP Right Cessation
-
1991
- 1991-10-04 US US08/039,084 patent/US5449447A/en not_active Expired - Fee Related
- 1991-10-04 WO PCT/BE1991/000071 patent/WO1992006231A2/fr not_active Application Discontinuation
- 1991-10-04 EP EP91916209A patent/EP0560771A1/fr not_active Withdrawn
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US2860092A (en) * | 1957-12-31 | 1958-11-11 | American Can Co | Electropickling process |
FR1488623A (fr) * | 1965-06-30 | 1967-07-13 | Bekaert Pvba Leon | Procédé et installation de revêtement d'acier |
AU4499468A (en) * | 1969-09-22 | 1971-03-25 | Australian Iron & Steel Pty. Limited | Improvements insteel strip pickling |
EP0202870A1 (fr) * | 1985-05-17 | 1986-11-26 | David Reznik | Appareil et procédé pour traitement anodique |
EP0209168A1 (fr) * | 1985-07-12 | 1987-01-21 | N.V. Bekaert S.A. | Procédé et dispositif pour le nettoyage par décapage électrochimique en utilisant un courant alternatif d'une fréquence spécifiée |
Non-Patent Citations (1)
Title |
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Draht, vol. 33, no. 6, juin 1982, (Bamberg, DE), G. HASCHKE et al.: "Elektrolytische Reinigung von Stahldrähten in Geraddurchzugsanlagen", pages 384-387 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5449447A (en) * | 1990-10-08 | 1995-09-12 | Le Four Industriel Belge S.A. | Method and device for pickling and galvanizing |
EP0644276A1 (fr) * | 1993-09-17 | 1995-03-22 | Hitachi, Ltd. | Procédé et dispositif pour la fabrication et le décapage de tôles d'acier laminées à chaud |
CN1068389C (zh) * | 1993-09-17 | 2001-07-11 | 株式会社日立制作所 | 一种热轧带钢的制造方法及其设备 |
EP0695818A1 (fr) * | 1994-07-07 | 1996-02-07 | MANNESMANN Aktiengesellschaft | Procédé et dispositif pour traitement de surface électrolytique |
CN108624939A (zh) * | 2017-03-21 | 2018-10-09 | 宜兴北宸科技有限公司 | 节能环保垂直镀阶梯式连续电镀生产系统 |
Also Published As
Publication number | Publication date |
---|---|
US5449447A (en) | 1995-09-12 |
WO1992006231A3 (fr) | 1992-11-26 |
BE1005217A3 (fr) | 1993-06-01 |
EP0560771A1 (fr) | 1993-09-22 |
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