EP0663454B2 - Process for suppressing the zinc vaporisation during hot dip coating of a steel strip - Google Patents
Process for suppressing the zinc vaporisation during hot dip coating of a steel strip Download PDFInfo
- Publication number
- EP0663454B2 EP0663454B2 EP94112801A EP94112801A EP0663454B2 EP 0663454 B2 EP0663454 B2 EP 0663454B2 EP 94112801 A EP94112801 A EP 94112801A EP 94112801 A EP94112801 A EP 94112801A EP 0663454 B2 EP0663454 B2 EP 0663454B2
- Authority
- EP
- European Patent Office
- Prior art keywords
- zinc
- steel strip
- suppressing
- dip coating
- gas atmosphere
- 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.)
- Expired - Lifetime
Links
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 23
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 15
- 239000010959 steel Substances 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title claims abstract description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims description 24
- 239000011701 zinc Substances 0.000 title claims description 23
- 238000003618 dip coating Methods 0.000 title claims description 5
- 238000009834 vaporization Methods 0.000 title claims 2
- 239000007789 gas Substances 0.000 claims abstract description 24
- 230000001681 protective effect Effects 0.000 claims abstract description 13
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims abstract description 3
- 229910001297 Zn alloy Inorganic materials 0.000 claims abstract 2
- 239000011248 coating agent Substances 0.000 claims abstract 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 23
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 12
- 239000001569 carbon dioxide Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000009434 installation Methods 0.000 claims 1
- 238000001704 evaporation Methods 0.000 abstract description 3
- 230000008020 evaporation Effects 0.000 abstract description 3
- 238000007654 immersion Methods 0.000 abstract 1
- 239000000155 melt Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000010494 dissociation reaction Methods 0.000 description 4
- 230000005593 dissociations Effects 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 2
- 241001474791 Proboscis Species 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000003197 gene knockdown Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000011144 upstream manufacturing 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
- 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
- C23C2/003—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
Definitions
- the invention relates to a method for suppression the formation of zinc vapor during hot dip coating a steel belt.
- EP 0 172 681 then contains the teaching in more detail limited amount of water vapor in the protective gas atmosphere in the trunk above the zinc bath surface.
- the inert or nitrogen gas introduced 250 to 4500 ppm water vapor and 1 to 8 Vol .-% hydrogen injected.
- Zinc oxide formed, which covers the zinc bath surface and a further zinc evaporation as a barrier layer prevented. In practice, this is known
- methods according to EP 0 172 681 have disadvantages.
- the increased water vapor content in the trunk leads surface defects in a large number of steels on the line.
- the decay of water molecules creates atomic hydrogen in the steel strip surface diffused. When cooling the dip coated Steel strip arise in the area of inclusion lines, in which the atomic hydrogen accumulates, bulges on the steel surface. This affect the flatness and appearance of the coated Steel surface and are intolerable.
- the invention is based on the object without the disadvantages described in EP 0 172 681 known method from zinc evaporation to suppress the zinc dip bath, in particular should by the measure to be taken, the one to be coated Steel strip in its quality will not be affected.
- the invention relates to a method according to independent claim 1; preferred embodiments are the subject of the dependent claims 2 and 3.
- the invention suggested that the protective gas atmosphere in the trunk above the zinc bath surface Carbon dioxide and a reducing gas, such as Contains hydrogen and / or carbon monoxide.
- a reducing gas such as Contains hydrogen and / or carbon monoxide.
- the proportion of carbon dioxide in the Atmosphere of the probosc is at least 0.05 to about 8 % By volume, preferably 0.5 to 4% by volume.
- the amount of hydrogen can up to 20 vol .-% that of carbon monoxide up to 10 vol .-%.
- the ratio of reducing ones Gas to carbon dioxide in the protective gas atmosphere of the trunk is at least 1: 1 i.e. So, an excess of reducing should be preferred Gas be present.
- a gas mixture consisting of nitrogen or an inert gas mixture and of carbon dioxide and a reducing gas is introduced into the trunk above the zinc bath surface.
- the individual gases of the mixture are fed into the proboscis through a feed pipe via conventional mass flow controllers.
- Zinc reacts with the carbon dioxide on the bath surface according to the chemical formula Zn + CO2 ⁇ ZnO + CO.
- the protective gas atmosphere in the trunk area is a reducing one Gas such as hydrogen or Carbon monoxide, contained in excess as a regulatory. This prevents the dissociation of carbon dioxide produced with the Steel strip surface reacts with the formation of oxide.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Coating With Molten Metal (AREA)
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Unterdrükkung der Zinkdampfbildung beim Schmelztauchbeschichten eines Stahlbandes.The invention relates to a method for suppression the formation of zinc vapor during hot dip coating a steel belt.
Beim kontinuierlichen Schmelztauchbeschichten von Stahlbändern gelangt das in mehreren Stufen vorbehandelte Stahlband über einen Rüssel in das mit flüssigem Zink gefüllte Becken der Schmelztauchbeschichtungsanlage. Aufgrund des hohen Dampfdruckes von Zink über der flüssigen Phase verdampfen von der Badoberfläche im Rüssel verhältnismäßig große Mengen an Zink, wenn man nicht geeignete Gegenmaßnahmen trifft. Der Zinkdampf strömt dann entgegen der Bandlaufrichtung und sublimiert an den kühleren Rüsselwänden oder spätestens an den Wänden im Bereich der vorgeschalteten Kühlzone. Das hat zur Folge, daß sich zum einen die Wände dieser Anlagenbereiche in erheblichem Maße mit Zinksublimat bedecken, wodurch häufige Reinigung erforderlich wird. Störender sind aber abgelagerte Zinkstaubpartikel, die sich während des Betriebs von den Wänden des Rüssels, an denen sie sich zunächst abgelagert hatten, ablösen und auf dem Stahlband niederschlagen. Dort führen die Zinkstaubpartikel nach dem Beschichtungsprozeß zu störenden Oberflächenfehlern. Diese sind angesichts der gestiegenen Anforderungen der Kunden an die Qualität von oberflächenveredeltem Stahlband, z.B. beim Einsatz der Bleche für Außenhautteile von Kraftfahrzeugen, nicht akzeptabel.For continuous hot dip coating steel strips get the pretreated in several stages Steel tape over a trunk in the liquid Zinc-filled pools of the hot-dip coating system. Due to the high vapor pressure of Zinc above the liquid phase evaporate from the bath surface relatively large quantities in the trunk of zinc if you don't take appropriate countermeasures meets. The zinc vapor then flows in the opposite direction of the belt and sublime on the cooler trunk walls or at the latest on the walls in the area of the upstream Cooling zone. The result is that on the one hand, the walls of these plant areas to a considerable extent Cover measurements with zinc sublimate, making frequent Cleaning becomes necessary. But more annoying are deposited Zinc dust particles that accumulate during operation from the walls of the trunk, against which they are attached had initially deposited, peel off and on the steel belt knock down. The zinc dust particles lead there after the coating process to annoying surface defects. These are given the increased demands of the customer to the quality of surface refined Steel strip, e.g. when using the sheets for outer skin parts of motor vehicles, not acceptable.
Man hat bereits Maßnahmen getroffen, um der störenden Zinkdampfbildung entgegenzuwirken. So hat man zunächst durch eine Taupunktkontrolle des Schutzgases (Inertgas oder Stickstoff) im Rüssel oberhalb der Zinkbadoberfläche dafür gesorgt, daß möglichst wenig Wasserdampf vorhanden ist, der durch Dissoziation Sauerstoff abspaltet, der sich mit dem Zinkdampf zu Zinkoxid umsetzt. Man war lange der Meinung, daß die auftretenden Oberflächenfehler auf der Bildung von Zinkoxid beruhen. Als weitere Maßnahme hat man in begrenzter Menge Wasserstoff dem Inertgas zugemischt.Measures have already been taken to avoid the disruptive Counteract zinc vapor formation. So had first by checking the dew point of the Shielding gas (inert gas or nitrogen) in the trunk above the zinc bath surface ensured that as possible little water vapor is present due to dissociation Cleaves oxygen that is released with the zinc vapor converts to zinc oxide. For a long time it was believed that the surface defects occurring on the Formation of zinc oxide based. As another measure you have the inert gas in a limited amount of hydrogen admixed.
Die EP 0 172 681 enthält dann die Lehre, in genau begrenzter Menge Wasserdampf in die Schutzgasatmosphäre im Rüssel oberhalb der Zinkbadoberfläche einzuleiten. Mit dem eingeleiteten Inert- oder Stickstoffgas wurden 250 bis 4500 ppm Wasserdampf und 1 bis 8 Vol.-% Wasserstoff eingeblasen. Durch Dissoziation des Wasserdampfes wurde auf der Zinkbadoberfläche Zinkoxid gebildet, welches die Zinkbadoberfläche abdeckt und als Sperrschicht eine weitere Zinkverdampfung verhindert. In der Praxis weist dieses bekannte Verfahren gemäß EP 0 172 681 jedoch Nachteile auf. Der angehobene Wasserdampfgehalt im Rüssel führt bei einer Vielzahl von Stählen zu Oberflächenfehlern am Band. Durch den Zerfall von Wassermolekülen entsteht atomarer Wasserstoff, der in die Stahlbandoberfläche eindiffundiert. Beim Abkühlen des tauchbeschichteten Stahlbandes entstehen im Bereich von Einschlußzeilen, in denen sich der atomare Wassserstoff anlagert, Auswölbungen an der Stahloberfläche. Diese beeinträchtigen die Ebenheit und das Aussehen der beschichteten Stahloberfläche und sind nicht tolerierbar.EP 0 172 681 then contains the teaching in more detail limited amount of water vapor in the protective gas atmosphere in the trunk above the zinc bath surface. With the inert or nitrogen gas introduced 250 to 4500 ppm water vapor and 1 to 8 Vol .-% hydrogen injected. Through dissociation of water vapor was on the zinc bath surface Zinc oxide formed, which covers the zinc bath surface and a further zinc evaporation as a barrier layer prevented. In practice, this is known However, methods according to EP 0 172 681 have disadvantages. The increased water vapor content in the trunk leads surface defects in a large number of steels on the line. The decay of water molecules creates atomic hydrogen in the steel strip surface diffused. When cooling the dip coated Steel strip arise in the area of inclusion lines, in which the atomic hydrogen accumulates, bulges on the steel surface. This affect the flatness and appearance of the coated Steel surface and are intolerable.
Außerdem sind aufwendige Kontroll- und Steuerungsmaßnahmen erforderlich, um den Wasserdamofgehalt in den engen Grenzen einzustellen und durch kontrollierte Zufuhr aufrechtzuerhalten.In addition, there are complex control measures required to the water damof content set within the narrow limits and by maintain controlled supply.
Der Erfindung liegt nun die Aufgabe zugrunde, ohne die geschilderten Nachteile des aus der EP 0 172 681 bekannten Verfahrens die Zinkverdampfung aus dem Zinktauchbad zu unterdrücken, insbesondere soll durch die zu treffende Maßnahme das zu beschichtende Stahlband in seiner Qualität nicht beeinträchtigt werden.The invention is based on the object without the disadvantages described in EP 0 172 681 known method from zinc evaporation to suppress the zinc dip bath, in particular should by the measure to be taken, the one to be coated Steel strip in its quality will not be affected.
Gegenstand des Erfindung ist ein Verfahren nach dem unabhängigen Anspruch 1; bevorzugte Ausführungsformen sind Gegenstand der abhängigen Ansprüche 2 und 3.The invention relates to a method according to independent claim 1; preferred embodiments are the subject of the dependent claims 2 and 3.
Zur Lösung der gestellten Aufgabe wird erfindungsgemäß vorgeschlagen, daß die Schutzgasatmosphäre im Rüssel oberhalb der Zinkbadoberfläche zusätzlich Kohlendioxid sowie ein reduzierendes Gas, wie beispielsweise Wasserstoff und/oder Kohlenmonoxid enthält. Bevorzugt soll der Anteil von Kohlendioxid in der Atmosphäre des Rüssels mindestens 0,05 bis etwa 8 Vol.-%, bevorzugt 0,5 bis 4 Vol.-%, betragen. Der Anteil von Wasserstoff kann bis 20 Vol.-%, der von Kohlenmonoxid bis 10 Vol.-% betragen. Das Verhältnis von reduzierendern Gas zu Kohlendioxid in der Schutzgasatmosphäre des Rüssels beträgt, mindestens 1:1 d.h. also, bevorzugt sollte ein Überschuß an reduzierendem Gas vorhanden sein.To solve the problem, the invention suggested that the protective gas atmosphere in the trunk above the zinc bath surface Carbon dioxide and a reducing gas, such as Contains hydrogen and / or carbon monoxide. Preferably, the proportion of carbon dioxide in the Atmosphere of the proboscis at least 0.05 to about 8 % By volume, preferably 0.5 to 4% by volume. The amount of hydrogen can up to 20 vol .-% that of carbon monoxide up to 10 vol .-%. The ratio of reducing ones Gas to carbon dioxide in the protective gas atmosphere of the trunk is at least 1: 1 i.e. So, an excess of reducing should be preferred Gas be present.
Nach der Erfindung wird in den Rüssel oberhalb der
Zinkbadoberfläche ein Gasgemisch, bestehend aus
Stickstoff oder einem Inertgasgemisch sowie aus Kohlendioxid
und einem reduzierenden Gas eingeleitet. Die
einzelnen Gase des Gemisches werden über herkömmliche
Massendurchflußregler durch ein Zuleitungsrohr in
den Rüssel eingespeist. An der Badoberfläche reagiert
Zink mit dem Kohlendioxid nach der chemischen Formel
Um eine Bildung überschüssigen Sauerstoffs bei der Dissoziation von Kohlendioxid zu vermeiden, muß die Schutzgasatmosphäre im Rüsselbereich ein reduzierendes Gas, wie beispielsweise Wasserstoff oder Kohlenmonoxid, als Regulativ im Überschuß enthalten. Hierdurch wird also verhindert, daß aus der Dissoziation von Kohlendioxid entstehender Stauerstoff mit der Stahlbandoberfläche unter Oxidbildung reagiert.To contribute to the formation of excess oxygen to avoid the dissociation of carbon dioxide the protective gas atmosphere in the trunk area is a reducing one Gas such as hydrogen or Carbon monoxide, contained in excess as a regulatory. This prevents the dissociation of carbon dioxide produced with the Steel strip surface reacts with the formation of oxide.
Aufgrund der erfindungsgemäßen Verfahrensweise kann auf eine Befeuchtung der Schutzgasatmosphäre mit Wasserdampf verzichtet werden. Dadurch ist das erfindungsgemäße Verfahren gegenüber der bekannten Taupunktsteuerung der Schutzgasatmosphäre bzw. der gesteuerten Wasserdampfzufuhr zur Schutzgasatmosphäre einfacher und kostengünstiger durchführbar.Because of the procedure according to the invention can humidify the protective gas atmosphere with water vapor. This is the inventive Process compared to the known Dew point control of the protective gas atmosphere or controlled water vapor supply to the protective gas atmosphere easier and cheaper to carry out.
Claims (3)
- A process for suppressing zinc vaporisation during the hot dip coating of a steel strip with zinc or zinc alloys, characterised in the inlet zone of the zinc coating installation a protective gas atmosphere is maintained consisting of a mixture of an inert gas with hydrogen and/or carbon monoxide as reducing gases and additional carbon dioxide, wherein the ratio of reducing gases and additional carbon dioxide, wherein the ration of reducing gases to carbon dioxide in the protective gas atmosphere is at least 1:1.
- A process according to Claim 1 characterised in that 0.05 to 8% by volume preferably 0.5 to 4% by volume CO2 are admixed to the protective gas atmosphere.
- A process according to Claims 1 or 2 characterised in that up to 20% H2 and up to 10% CO are added to the protective gas atmosphere.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4400886 | 1994-01-14 | ||
| DE4400886A DE4400886C2 (en) | 1993-07-24 | 1994-01-14 | Process for suppressing the formation of zinc vapor during hot dip coating of a steel strip |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0663454A1 EP0663454A1 (en) | 1995-07-19 |
| EP0663454B1 EP0663454B1 (en) | 1998-04-15 |
| EP0663454B2 true EP0663454B2 (en) | 2002-01-02 |
Family
ID=6507895
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP94112801A Expired - Lifetime EP0663454B2 (en) | 1994-01-14 | 1994-08-17 | Process for suppressing the zinc vaporisation during hot dip coating of a steel strip |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP0663454B2 (en) |
| AT (1) | ATE165121T1 (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1319282A (en) * | 1970-06-10 | 1973-06-06 | Kuei Fan Yu | Hot dip galvanizing |
| US4466999A (en) * | 1983-10-28 | 1984-08-21 | United States Steel Corporation | Atmospheric gas practice for hot-dip coating of metals |
| JPS6230864A (en) * | 1985-07-31 | 1987-02-09 | Sumitomo Metal Ind Ltd | Hot dip metal coating apparatus |
| US5472740A (en) * | 1990-10-11 | 1995-12-05 | Totoku Electric Co., Ltd. | Process of producing a hot dipped wire from a base wire, with the absence of iron-based, iron oxide-based and iron hydroxide-based minute particles on surfaces of the base wire |
-
1994
- 1994-08-17 EP EP94112801A patent/EP0663454B2/en not_active Expired - Lifetime
- 1994-08-17 AT AT94112801T patent/ATE165121T1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| EP0663454A1 (en) | 1995-07-19 |
| ATE165121T1 (en) | 1998-05-15 |
| EP0663454B1 (en) | 1998-04-15 |
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