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EP1100982B1 - Stripper for special steel - Google Patents

Stripper for special steel Download PDF

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Publication number
EP1100982B1
EP1100982B1 EP99942796A EP99942796A EP1100982B1 EP 1100982 B1 EP1100982 B1 EP 1100982B1 EP 99942796 A EP99942796 A EP 99942796A EP 99942796 A EP99942796 A EP 99942796A EP 1100982 B1 EP1100982 B1 EP 1100982B1
Authority
EP
European Patent Office
Prior art keywords
weight
acid
pickling
compound
hydrogen fluoride
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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
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EP99942796A
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German (de)
French (fr)
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EP1100982A1 (en
Inventor
Eckart SCHÖNFELDER
Günther Schwane
Harald Werner
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Chemetall GmbH
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Chemetall GmbH
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel
    • C23G1/086—Iron or steel solutions containing HF
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/025—Cleaning or pickling metallic material with solutions or molten salts with acid solutions acidic pickling pastes

Definitions

  • the invention relates to a wetting and emulsifying agent-free aqueous pickling agent for stainless steels based on sulfuric acid or phosphoric acid and hydrogen fluoride.
  • the most important acids for pickling stainless steels or Acid mixtures are hydrofluoric acid, hydrofluoric acid / nitric acid, Hydrofluoric acid / sulfuric acid with some considerable additives of iron III compounds already in the starting phase of Mordant.
  • Another method is a so-called single bath degreasing and pickling of iron containing or objects made of it. It works with solutions the acids, wetting agents and / or emulsifiers as well Oxidizing agents aromatic, water soluble Nitro compounds, e.g. Nitrobenzenesulfonate included (DE-A-25 07 059).
  • Single-bath degreasing and pickling leads to the entry of oils or fats in the Pickling bath, which makes the pickling process unpredictable Way is affected. In particular, training prevents a uniform pickling pattern.
  • the content of Wetting agents and / or emulsifiers also make it more difficult Preparation of the rinse and Wastewater.
  • the object of the invention is an aqueous mordant for To provide stainless steels that are known, in particular aforementioned disadvantages, does not have, and is procedurally simple and inexpensive to carry out.
  • the task is solved by the mordant of the beginning formulated according to the invention in such a way is that it (each as 100 wt .-% substance) 1.5 to 16% by weight sulfuric acid or 2.0 to 30% by weight Phosphoric acid and 0.5 to 14 wt .-% hydrogen fluoride and 0.5 to 15.5% by weight of acid-soluble aromatic Nitro compound contains no iron III compound is supplied and only in the start phase iron II Oxidizing agent oxidizing to iron III are supplied can.
  • mordants according to the invention can also be used in the Starting phase without iron II oxidizing to iron III Oxidizing agents are used.
  • iron II oxidizing to iron III Oxidizing agents are used.
  • small amounts of oxidizing agents admit based on peroxide compounds for example 0.05% by weight.
  • the mordant according to the invention can be used as a bath stain Spray or tweezers are used.
  • a pickling agent which, when used as a bath pickle, contains 5.0 to 11% by weight of sulfuric acid or 8.0 to 20% by weight of phosphoric acid and 4.0 to 10% by weight. Contains hydrogen fluoride and 4.5 to 11 wt .-% acid-soluble aromatic nitro compound.
  • the pickling agent with the aforementioned concentration ranges is characterized by a sufficiently high pickling rate without the base material being attacked. In addition, it is particularly inexpensive.
  • magnesium in the amounts mentioned will Mordant transferred to a thixotropic gel. This will the order of a sufficient amount for the Guaranteed pickling process required pickling agent. It is particularly advantageous to use the magnesium in metallic Form, as magnesium oxide, hydroxide, carbonate or sulfate add.
  • the mordant in its application as Spray stain with a content of 9.5 to 15.5% by weight Sulfuric acid or 15.0 to 30.0% by weight phosphoric acid, and 4.0 to 11.0 wt% hydrogen fluoride, 4.5 to 11.5 % By weight acid-soluble aromatic nitro compound and 2.5 up to 4.5% by weight of magnesium compound (calculated as Mg) use.
  • mordant in its application as a brush stain 12.0 to 16.0% by weight sulfuric acid or 18.0 to 30.0% by weight Phosphoric acid and 4.5 to 12.0% by weight of hydrogen fluoride, 2.5 to 9.5% by weight of acid-soluble aromatic Nitro compound and 3.0 to 5.5% by weight magnesium compound (calc. as Mg).
  • Suitable acid-soluble aromatic nitro compounds are those that have at least one nitro and at least one acidic group, especially a carboxyl or Have sulfonic acid group. It is particularly advantageous it, as an acid-soluble aromatic nitro compound Use m-nitrobenzenesulfonate and / or 3-nitrophthalate.
  • the temperatures at which the invention Pickling agents are used depending on the type of Different application. When used as a bath stain it is set to a value in the range of 15 to 80 ° C. Depending on the degree of scaling or Oxide coating of the pickling material 5 to 90 min., The shorter ones Pickling times for the higher pickling temperatures and the longer pickling times for the lower pickling temperatures be valid.
  • the pickling agent When using the pickling agent as a spray or Brush stains are usually through the pickling temperatures the prevailing room or ambient temperatures specified. They are generally between 15 and 35 ° C. The required pickling time is about 15 to 180 min.
  • the plate pairs were spaced 2 minutes apart. optically on Descaling the weld and removing Tarnished colors checked.
  • the sheet pair made of material 1.4511 was after 10 min made of material 1.4462 after 24 min. clean.
  • the clear, viscous liquid obtained was applied to metal sheets of steel grade 1.4301, which is a hand drawn Welded seam, with a pressure of 6 bar sprayed.
  • the obtained 1 to 2 mm thick film flowed due to its thixotropy also on vertical surfaces Not.
  • the spray stain was rinsed.
  • the weld was descaled.
  • the entire sheet surface was uniformly light and weak angebeizt.
  • a non-flowable, opaque paste was created that with a brush on the weld of a sheet of metal Stainless steel quality 1.4571 in a thickness of 2 to 3 mm was applied.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Detergent Compositions (AREA)
  • Glass Compositions (AREA)
  • Catalysts (AREA)

Abstract

The inventive aqueous pickling agent on the basis of sulfuric acid or phosphoric acid and hydrogen fluoride for stainless steels, which pickling agent is free of wetting and emulsifying agents, contains (each as 100 wt-% substance) 1.5 to 16 wt-% sulfuric acid or 2.0 to 30 wt-% phosphoric acid as well as 0.5 to 14 wt-% hydrogen fluoride and 0.5 to 15.5 wt-% acid-soluble aromatic nitro compound. An iron(III) compound is not supplied to said pickling agent. Merely in the starting phase, an oxidizing agent can be supplied, which oxidizes iron(II) to form iron(III). As acid-soluble aromatic nitro compound m-nitrobenzene sulfonate and/or 3-nitrophthalate are particularly advantageous. The inventive pickling agent can be used as bath pickle and -when adding 2.5 to 5.5 wt-% magnesium and/or magnesium compound (calculated as Mg)-also as spraying pickle or brush pickle.

Description

Die Erfindung betrifft ein netz- und emulgiermittelfreies, wäßriges Beizmittel für Edelstähle auf Basis Schwefelsäure oder Phosphorsäure und Fluorwasserstoff.The invention relates to a wetting and emulsifying agent-free aqueous pickling agent for stainless steels based on sulfuric acid or phosphoric acid and hydrogen fluoride.

Es ist allgemein üblich, Edelstähle mit verschiedenen Säuren oder Säuregemischen (Beizmitteln) zu beizen, um Korrosionsprodukte sowie z. B. beim Schweißen entstandene Zunderschichten oder Anlauffarben zu entfernen. Die Beizmittel können dabei als Badbeize oder aber - insbesondere bei großen Teilen oder örtlicher Oxidbildung - als Sprühbeize oder als Pinselbeize eingesetzt werden.It is common practice to use stainless steels with different Acids or acid mixtures (pickling agents) to pickle Corrosion products and z. B. created during welding Remove scale layers or tarnish. The Mordants can be used as bath stains or - especially with large parts or local oxide formation - can be used as a spray stain or as a brush stain.

Die zum Beizen von Edelstählen wichtigsten Säuren oder Säuregemische sind Flußsäure, Flußsäure/Salpetersäure, Flußsäure/Schwefelsäure mit zum Teil erheblichen Zusätzen an Eisen III-Verbindungen bereits in der Startphase des Beizmittels. Zum Teil enthalten die Beizmittel Wasserstoffperoxid, mit dessen Hilfe die durch den Beizangriff in Lösung gehenden Eisen II-Ionen zu Eisen III-Ionen oxidiert werden. Beispiele derartiger Beizmittel sind in WO 87/01 739, DE-A-38 25 857, DE-A-44 17 284, EP-A-505 605 und EP-A-596 273 beschrieben.The most important acids for pickling stainless steels or Acid mixtures are hydrofluoric acid, hydrofluoric acid / nitric acid, Hydrofluoric acid / sulfuric acid with some considerable additives of iron III compounds already in the starting phase of Mordant. Some contain the mordants Hydrogen peroxide, with the help of which the Pickling attack in solution iron II ions to iron III ions be oxidized. Examples of such mordants are in WO 87/01 739, DE-A-38 25 857, DE-A-44 17 284, EP-A-505 605 and EP-A-596 273.

Den bekannten Beizmitteln haften die unterschiedlichsten Nachteile an. Ein Nachteil ist häufig die geringe Beizgeschwindigkeit.Auch kann sich eine zu hohe Beizgeschwindigkeit nachteilig auswirken, wenn in Beizanlagen Taktzeiten vorgegeben sind. Dies gilt insbesondere für Flußsäure/Salpetersäure -Beizmittel. Darüberhinaus treten bei diesen Beizmitteln mit hohen Säurekonzentrationen aus den Beizbädern gesundheitsgefährdende Dämpfe aus, die abgesaugt und in einer Waschanlage behandelt werden müssen. Wegen der großen Löslichkeit der Nitrate ist zudem die Aufbereitung der im Beizprozeß anfallenden Spül- und Abwässer schwierig. Niedrig konzentrierte Beizmittel auf Basis Flußsäure/Salpetersäure sind zudem mit dem Nachteil behaftet, daß dunkle fleckige und nicht die an sich erwünschten metallisch hellen Metalloberflächen entstehen. Beizmittel, die zur Einstellung des erforderlichen RedoxPotentials bereits in der Startphase beträchtliche Zusätze von Fe III-Verbindung aufweisen, sind insofern mit dem Mangel behaftet, daß sich das Aufnahmevermögen von aus dem Oxidbelag des Beizgutes stammenden Fe II bzw. Fe III entsprechend der zugesetzten Fe III-Menge reduziert.A wide variety of adhesives adhere to the known pickling agents Disadvantages. The disadvantage is often the low one Pickling speed, too high Adversely affect pickling speed when in Pickling plants cycle times are specified. this applies especially for hydrofluoric acid / nitric acid mordants. In addition, these mordants occur with high Acid concentrations from the pickling baths harmful vapors from which are sucked off and in must be treated in a car wash. Because of the big one The solubility of the nitrates is also the processing of the Pickling process of rinsing water and waste water difficult. Low concentrated mordants based Hydrofluoric acid / nitric acid are also disadvantageous afflicted that dark blotchy and not that in itself desired metallic bright metal surfaces arise. Pickling agent used to set the required redox potential considerable additions already in the start-up phase of Fe III compound are so far with the Deficiency affecting that the absorption capacity from the Oxide coating of the Fe II or Fe III originating from the pickling material reduced according to the amount of Fe III added.

Die Verfahren mit Beizmitteln auf Basis Schwefelsäure/Flußsäure/Wasserstoffperoxid, die im Tauchen Anwendung finden und bei denen es in der Regel nötig ist, ein bestimmtes Redox-Potential aufrechtzuerhalten, sind vergleichsweise aufwendig in der Verfahrensführung, so daß sie insbesondere für kleinere Beizereien nicht in Betracht kommen. Weitere Nachteile sind, daß sich das Wasserstoffperoxid im Beizmittel relativ leicht zersetzt und bei geringem Peroxid-Zusatz eine nur langsame Oxidauflösung, d.h. geringe Beizgeschwindigkeit erhalten wird.The process with mordants based Sulfuric acid / hydrofluoric acid / hydrogen peroxide used in diving Find application and where it is usually necessary maintain a certain redox potential comparatively complex to run, so that especially not for smaller pickling plants come. Other disadvantages are that Hydrogen peroxide decomposes relatively easily in the mordant and with a low peroxide addition, only a slow one Oxide dissolution, i.e. obtained low pickling speed becomes.

Ein weiteres Verfahren besteht in einem sogenannten einbadigen Entfetten und Beizen von Eisen enthaltenden oder daraus bestehenden Gegenständen. Es arbeitet mit Lösungen, die Säuren, Netz-und/oder Emulgiermittel sowie als Oxidationsmittel aromatische, wasserlösliche Nitroverbindungen, wie z.B. Nitrobenzolsulfonat, enthalten ( DE-A-25 07 059 ). Das einbadige Entfetten und Beizen führt zwangsweise zum Eintrag von Ölen oder Fetten in das Beizbad, wodurch der Beizprozeß in nicht kalkulierbarer Weise beeinflußt wird. Insbesondere wird die Ausbildung eines gleichmäßigen Beizbildes verhindert. Der Gehalt an Netz-und/oder Emulgiermitteln erschwert zudem die Aufbereitung der im Beizprozeß anfallenden Spül-und Abwässer.Another method is a so-called single bath degreasing and pickling of iron containing or objects made of it. It works with solutions the acids, wetting agents and / or emulsifiers as well Oxidizing agents aromatic, water soluble Nitro compounds, e.g. Nitrobenzenesulfonate included (DE-A-25 07 059). Single-bath degreasing and pickling leads to the entry of oils or fats in the Pickling bath, which makes the pickling process unpredictable Way is affected. In particular, training prevents a uniform pickling pattern. The content of Wetting agents and / or emulsifiers also make it more difficult Preparation of the rinse and Wastewater.

Schließlich ist aus der US-Patentschrift 2 698 781 ein als zum Auflösen von Metallen bezeichnetes Verfahren bekannt, das mit wäßrigen, eine aromatische Nitroverbindung enthaltenden starken Säuren arbeitet. Unter Berücksichtigung der Beispiele ist dieses Verfahren in erster Linie zur Behandlung von nickelplattiertem Kupfer sowie Kupfer und Blei bestimmt. Lediglich in einem Beispiel ist das Beizen von Edelstählen mit einem Schwefelsäure, m-Nitro-Benzolsulfonsäure und Fluorwasserstoffsäure enthaltenden Beizbad beschrieben, wobei die Schwefelsäurekonzentration 200 g/l beträgt. Beizbäder mit einer derartig hohen Schwefelsäurekonzentration arbeiten jedoch vergleichsweise langsam, so daß die Durchsatzleistung gering ist. Finally, from US Pat. No. 2,698,781 an as known method for dissolving metals, that with aqueous, an aromatic nitro compound containing strong acids works. Under Taking into account the examples, this procedure is in primarily for the treatment of nickel-plated copper as well as copper and lead. Just one example is pickling stainless steels with a sulfuric acid, m-nitro-benzenesulfonic acid and hydrofluoric acid containing pickling bath described, the Sulfuric acid concentration is 200 g / l. Pickling baths with work with such a high sulfuric acid concentration however comparatively slowly, so that the Throughput is low.

Aufgabe der Erfindung ist, ein wäßriges Beizmittel für Edelstähle bereitzustellen, das die bekannten, insbesondere vorgenannten Nachteile, nicht aufweist, sowie verfahrensmäßig einfach und kostengünstig durchführbar ist.The object of the invention is an aqueous mordant for To provide stainless steels that are known, in particular aforementioned disadvantages, does not have, and is procedurally simple and inexpensive to carry out.

Die Aufgabe wird gelöst, indem das Beizmittel der eingangs genannten Art entsprechend der Erfindung derart formuliert wird, daß es (jeweils als 100 Gew.-%-ige Substanz) 1,5 bis 16 Gew.-% Schwefelsäure oder 2,0 bis 30 Gew.-% Phosphorsäure sowie 0,5 bis 14 Gew.-% Fluorwasserstoff und 0,5 bis 15.5 Gew.-% säurelösliche aromatische Nitroverbindung enthält, dem keine Eisen III-verbindung zugeführt wird und dem lediglich in der Startphase Eisen II zu Eisen III oxidierendes Oxidationsmittel zugeführt werden kann.The task is solved by the mordant of the beginning formulated according to the invention in such a way is that it (each as 100 wt .-% substance) 1.5 to 16% by weight sulfuric acid or 2.0 to 30% by weight Phosphoric acid and 0.5 to 14 wt .-% hydrogen fluoride and 0.5 to 15.5% by weight of acid-soluble aromatic Nitro compound contains no iron III compound is supplied and only in the start phase iron II Oxidizing agent oxidizing to iron III are supplied can.

Das zur Durchführung des Beizprozesses eingesetzte erfindungsgemäße Beizmittel kann prinzipiell auch in der Startphase ohne Eisen II zu Eisen III oxidierendes Oxidationsmittel zur Anwendung gelangen. Zur Aktivierung des frisch angesetzten Beizmittels kann es jedoch vorteilhaft sein, geringe Mengen Oxidationsmittel zuzugeben, auf Peroxidverbindungen bezogen beispielsweise 0,05 Gew.-%.The one used to carry out the pickling process In principle, mordants according to the invention can also be used in the Starting phase without iron II oxidizing to iron III Oxidizing agents are used. To activate of the freshly prepared mordant, however, it can be advantageous, small amounts of oxidizing agents admit based on peroxide compounds for example 0.05% by weight.

Das erfindungsgemäße Beizmittel kann als Badbeize, als Sprüh- oder als Pinzelbeize zur Anwendung gelangen.The mordant according to the invention can be used as a bath stain Spray or tweezers are used.

Infolge seiner Freiheit am Netz- und Emulgiermitteln ist darauf zu achten, daß das Beizgut durch das Beizmittel vollständig benetzbar ist. Sofern auf dem Beizgut befindliche Öl- oder Fettreste die vollständige Benetzbarkeit beeinträchtigen, ist eine vorherige Reinigung bzw. Entfettung mit den üblichen Reinigern und eine gründliche Wasserspülung dem Beizprozeß vorzuschalten.As a result of its freedom in wetting and emulsifying agents to ensure that the pickling material is removed by the pickling agent is completely wettable. If on the pickling any oil or grease residues Impact wettability is prior cleaning or degreasing with the usual cleaners and a to precede the pickling process with thorough water rinsing.

Gemäß einer besonders bevorzugten Ausgestaltung der Erfindung gelangt ein Beizmittel zum Einsatz, das in seiner Anwendung als Badbeize 5,0 bis 11 Gew.-% Schwefelsäure oder 8,0 bis 20 Gew.-% Phosphorsäure sowie 4,0 bis 10 Gew.-% Fluorwasserstoff und 4,5 bis 11 Gew.-% säurelösliche aromatische Nitroverbindung enthält.
Das Beizmittel mit den vorgenannten Konzentrationsbereichen zeichnet sich durch eine hinreichend hohe Beizgeschwindigkeit aus, ohne daß das Grundmaterial angegriffen wird. Darüberhinaus ist es kostenmäßig besonders günstig.According to a particularly preferred embodiment of the invention, a pickling agent is used which, when used as a bath pickle, contains 5.0 to 11% by weight of sulfuric acid or 8.0 to 20% by weight of phosphoric acid and 4.0 to 10% by weight. Contains hydrogen fluoride and 4.5 to 11 wt .-% acid-soluble aromatic nitro compound.
The pickling agent with the aforementioned concentration ranges is characterized by a sufficiently high pickling rate without the base material being attacked. In addition, it is particularly inexpensive.

Bei seiner Anwendung als Sprüh- oder Pinzelbeize enthält des Beizmittel vorzugsweise 2,5 bis 5,5 Gew % Magnesiumverbindung ( ber. als Mg ).Contains when used as a spray or tweezer of the mordant preferably 2.5 to 5.5% by weight Magnesium compound (calc. As Mg).

Durch Zugabe von Magnesium in den genannten Mengen wird das Beizmittel in ein thixotropes Gel überführt. Hierdurch wird der Auftrag einer ausreichenden Menge des für den Beizprozeß erforderlichen Beizmittels gewährleistet. Besonders vorteilhaft ist es, das Magnesium in metallischer Form, als Magnesiumoxid, -hydroxid, -carbonat oder -sulfat zuzusetzen.The addition of magnesium in the amounts mentioned will Mordant transferred to a thixotropic gel. This will the order of a sufficient amount for the Guaranteed pickling process required pickling agent. It is particularly advantageous to use the magnesium in metallic Form, as magnesium oxide, hydroxide, carbonate or sulfate add.

Demzufolge sieht eine bevorzugte Ausgestaltung der Erfindung vor, das Beizmittel in seiner Anwendung als Sprühbeize mit einem Gehalt von 9,5 bis 15,5 Gew % Schwefelsäure oder 15,0 bis 30,0 Gew.-% Phosphorsäure, sowie 4,0 bis 11,0 Gew.-% Fluorwasserstoff, 4,5 bis 11,5 Gew.-% säurelösliche aromatische Nitroverbindung und 2,5 bis 4,5 Gew.-% Magnesiumverbindung (ber. als Mg) einzusetzen.Accordingly, a preferred embodiment of the Invention before, the mordant in its application as Spray stain with a content of 9.5 to 15.5% by weight Sulfuric acid or 15.0 to 30.0% by weight phosphoric acid, and 4.0 to 11.0 wt% hydrogen fluoride, 4.5 to 11.5 % By weight acid-soluble aromatic nitro compound and 2.5 up to 4.5% by weight of magnesium compound (calculated as Mg) use.

In einer weiteren bevorzugten Ausführungsform der Erfindung enthält das Beizmittel in seiner Anwendung als Pinselbeize 12,0 bis 16,0 Gew % Schwefelsäure oder 18,0 bis 30.0 Gew.-% Phosphorsäure sowie 4,5 bis 12,0 Gew.-% Fluorwasserstoff, 2,5 bis 9,5 Gew.-% säurelösliche aromatische Nitroverbindung und 3,0 bis 5,5 Gew.-% Magnesiumverbindung (ber. als Mg).In a further preferred embodiment of the invention contains the mordant in its application as a brush stain 12.0 to 16.0% by weight sulfuric acid or 18.0 to 30.0% by weight Phosphoric acid and 4.5 to 12.0% by weight of hydrogen fluoride, 2.5 to 9.5% by weight of acid-soluble aromatic Nitro compound and 3.0 to 5.5% by weight magnesium compound (calc. as Mg).

Geeignete säurelösliche aromatische Nitroverbindungen sind solche, die am Benzolring mindestens eine Nitro- und mindestens eine saure Gruppe, insbesondere eine Carboxyloder Sulfonsäuregruppe aufweisen. Besonders vorteilhaft ist es, als säurelösliche aromatische Nitroverbindung m-Nitrobenzolsulfonat und/oder 3-Nitrophthalat einzusetzen.Suitable acid-soluble aromatic nitro compounds are those that have at least one nitro and at least one acidic group, especially a carboxyl or Have sulfonic acid group. It is particularly advantageous it, as an acid-soluble aromatic nitro compound Use m-nitrobenzenesulfonate and / or 3-nitrophthalate.

Die Temperaturen, bei denen die erfindungsgemäßen Beizmittel zum Einsatz kommen, sind je nach Art der Anwendung verschieden. Bei Anwendung als Badbeize werden sie auf einen Wert im Bereich von 15 bis 80°C eingestellt. Die Beizdauer beträgt je nach Grad der Verzunderung bzw. Oxidbelag des Beizgutes 5 bis 90 min., wobei die kürzeren Beizzeiten für die höheren Beiztemperaturen und die längeren Beizzeiten für die tieferen Beiztemperaturen gelten. Bei Anwendung des Beizmitteis als Sprüh- oder Pinselbeize sind die Beiztemperaturen in der Regel durch die herrschenden Raum- oder Umgebungstemperaturen vorgegeben. Sie liegen im allgemeinem zwischen 15 und 35°C. Die erforderliche Beizdauer beträgt etwa 15 bis 180 min.The temperatures at which the invention Pickling agents are used depending on the type of Different application. When used as a bath stain it is set to a value in the range of 15 to 80 ° C. Depending on the degree of scaling or Oxide coating of the pickling material 5 to 90 min., The shorter ones Pickling times for the higher pickling temperatures and the longer pickling times for the lower pickling temperatures be valid. When using the pickling agent as a spray or Brush stains are usually through the pickling temperatures the prevailing room or ambient temperatures specified. They are generally between 15 and 35 ° C. The required pickling time is about 15 to 180 min.

Mit Hilfe des erfindungsgemäßen Beizmittels ist ein verfahrensmäßig einfacher und kostengünstiger Beizprozeß durchführbar. Infolge des angestrebten und mit den erfindungsgemäßen Beizmittel erzielten mäßigen Beizabtrages werden helle samtige Oberflächen erzielt. Die Aufbereitung der Spül- und Abwässer gestaltet sich einfach, da die Beizmittelkomponenten mit z.B. Kalkmilch als schwerlösliche Calciumverbindungen ausgefällt und abgetrennt werden können.With the help of the mordant according to the invention is a procedurally simple and inexpensive pickling process feasible. As a result of the desired and with the Pickling agents according to the invention achieved moderate pickling removal bright, velvety surfaces are achieved. The preparation the rinsing and waste water is easy because the Mordant components with e.g. Lime milk as poorly soluble Calcium compounds are precipitated and separated can.

Die Erfindung wird anhand der nachfolgenden Beispiele näher erläutertThe invention is illustrated by the following examples explained

Beispiel 1example 1

Zur Ermittlung des Materialabtrages und der Oberflächenbeschaffenheit wurden metallisch reine Bleche der Edelstahlqualitäten 1.4541 und 1.4462 eine Stunde bei 30°C in den nachfolgend tabellarisch aufgeführten Beizmittelsystemen behandelt. Die %-Angaben verstehen sich als Gew.-%.To determine the material removal and the The surface texture was pure metal sheets stainless steel grades 1.4541 and 1.4462 for one hour 30 ° C in the table below Treatments systems treated. The% figures are understood as% by weight.

Die Ergebnisse sind hinsichtlich Materialabtrag in g/m2 in den Spalten zwei und drei, hinsichtlich Oberflächenbeschaffenheit in Spalte vier zusammengestellt. Nr. Beizmittel Materialabtrag Oberfläche 1.4541 1.4462 1. 15% HNO3/ 5% HF 55,8 27,1 silberhell, leicht rauh 2. 7% H2SO4/ 5% HF 18,9 6,9 grauschwarz belegte Oberfläche 3. 7% H2SO4/ 5% HF 1% H2O2 46,3 17,6 silberhell, leicht rauh 4. 7% H2SO4/ 5% HF 5% H2O2 41,1 16,2 silberhell, samtig 5. 7% H2SO4/ 5%HBF4 3% Fe-III-sulfat 9,2 0,1 hell, leicht fleckig 6. 7% H2SO4/ 5% HF 5% m-Nitrobenzolsulfonsäure 32,8 10,8 hell, samtig 7. 7% H2SO4/5HF 5% m-Nitrobenzol sulfonsäure 0,05% H2O2 in der Startphase 36,4 11,2 hell, samtig The results are shown in columns two and three with regard to material removal in g / m 2 and in column four with regard to surface properties. No. mordant material removal surface 1.4541 1.4462 1. 15% ENT 3 /5% HF 55.8 27.1 light silver, slightly rough Second 7% H 2 SO 4 /5% HF 18.9 6.9 gray-black coated surface Third 7% H 2 SO 4 /5% HF 1% H 2 O 2 46.3 17.6 light silver, slightly rough 4th 7% H 2 SO 4 /5% HF 5% H 2 O 2 41.1 16.2 silvery, velvety 5th 7% H 2 SO 4 /5% HBF 4 3% Fe III sulfate 9.2 0.1 bright, slightly stained 6th 7% H 2 SO 4 /5% HF 5% m-nitrobenzenesulfonic acid 32.8 10.8 light, velvety 7th 7% H 2 SO 4 / 5HF 5% m-nitrobenzene sulfonic acid 0.05% H 2 O 2 in the starting phase 36.4 11.2 light, velvety

Ein Vergleich der Ergebnisse zeigt, daß - mit Ausnahme des Beizmittels 4.) - allein die erfindungsgemäßen Beizmittel 6.) und 7.) die erwünschte helle, samtige Oberfläche entstehen ließen. Alle anderen führten zu leicht rauhen oder grauschwarz belegten, bzw. fleckigen Oberflächen. Dabei ist der Materialabtrag bei den Beizmitteln 6.) und 7.) vergleichsweise niedrig. A comparison of the results shows that - with the exception of the Pickling agents 4.) - only the pickling agents according to the invention 6.) and 7.) the desired light, velvety surface created. All others led to slightly rough or gray-black coated or stained surfaces. The material removal from the pickling agents 6) and 7.) comparatively low.

Beispiel 2Example 2

Je zwei, durch WIG-Verschweißen mit einer Längsnaht verbundene Stahlbleche mit den Abmessungen 45 x 140 mm aus den Edelstahlqualitäten 1.4541 und 1.4462 wurden in ein Beizmittel von 30°C getaucht, das aus

  • 5 Gew.-% Fluorwasserstoff
  • 7 Gew.-% Schwefelsäure und
  • 5,4 Gew.-% m-Nitrobenzolsulfonat
    (eingebracht als Na-Salz)
  • Rest Wasser
    • bestand.Two steel sheets with the dimensions 45 x 140 mm made of stainless steel qualities 1.4541 and 1.4462, connected by TIG welding with a longitudinal seam, were immersed in a pickling agent at 30 ° C
  • 5 wt% hydrogen fluoride
  • 7% by weight sulfuric acid and
  • 5.4% by weight of m-nitrobenzenesulfonate
    (introduced as Na salt)
  • Rest of water
    • duration.

    Die Blechpaare wurden im Abstand von 2 min. optisch auf Entzunderung der Schweißnaht und Entfernung von Anlauffarben geprüft.The plate pairs were spaced 2 minutes apart. optically on Descaling the weld and removing Tarnished colors checked.

    Das Blechpaar aus den Material 1.4511 war nach 10 min., das aus dem Material 1.4462 nach 24 min. sauber.The sheet pair made of material 1.4511 was after 10 min made of material 1.4462 after 24 min. clean.

    Beispiel 3Example 3

    Es wurde eine Sprühbeize aus

  • 14 Gew.-% Schwefelsäure (96 Gew.-%)
  • 19 Gew.-% Flußsäure (50 Gew.-%)
  • 12,1 Gew.-% MgCO3 und
  • 9 Gew.-% Na- m- Nitrobenzolsulfonat
  • Rest Wasser
    • formuliert.A spray stain was made
  • 14% by weight sulfuric acid (96% by weight)
  • 19% by weight hydrofluoric acid (50% by weight)
  • 12.1% by weight of MgCO 3 and
  • 9% by weight of Na-nitrobenzenesulfonate
  • Rest of water
    • formulated.

    Die erhaltene klare, viskose Flüssigkeit wurde auf Bleche der Stahlqualität 1.4301, die eine von Hand gezogene Schweißnaht aufwiesen, mit einem Druck von 6 bar aufgesprüht. Der erhaltene 1 bis 2 mm dicke Film verfloß infolge seiner Thixotropie auch auf vertikalen Flächen nicht.The clear, viscous liquid obtained was applied to metal sheets of steel grade 1.4301, which is a hand drawn Welded seam, with a pressure of 6 bar sprayed. The obtained 1 to 2 mm thick film flowed due to its thixotropy also on vertical surfaces Not.

    Nach einer Einwirkungszeit von 1h wurde die Sprühbeize abgespült. Die Schweißnaht war sauber entzundert. Die gesamte Blechoberfläche war einheitlich hell und schwach angebeizt.After an exposure time of 1 hour, the spray stain was rinsed. The weld was descaled. The entire sheet surface was uniformly light and weak angebeizt.

    Beispiel 4Example 4

    Es wurde eine Pinselbeize aus

  • 24 Gew.-% Phosphorsäure (85 Gew.-%)
  • 14 Gew.-% Flußsäure (70 Gew.-%)
  • 6,6 Gew.-% Magnesiumoxid und
  • 5 Gew.-% 3-Nitrophthalsäure
  • Rest Wasser
    • hergestellt.There was a brush stain
  • 24% by weight phosphoric acid (85% by weight)
  • 14% by weight of hydrofluoric acid (70% by weight)
  • 6.6 wt .-% magnesium oxide and
  • 5% by weight of 3-nitrophthalic acid
  • Rest of water
    • manufactured.

    Es entstand eine nicht mehr fließfähige, opake Paste, die mit einem Pinsel auf die Schweißnaht eines Bleches der Edelstahlqualität 1.4571 in einer Dicke von 2 bis 3 mm aufgebracht wurde.A non-flowable, opaque paste was created that with a brush on the weld of a sheet of metal Stainless steel quality 1.4571 in a thickness of 2 to 3 mm was applied.

    Nach 2 Stunden wurde die Beizpaste abgespült und die Schweißnaht mit einem scharfen Wasserstrahl abgespritzt. Die Schweißnaht war hell und blank, die Oxidschicht vollständig entfernt und das Grundmaterial frei von einem sichtbaren Beizangriff.After 2 hours the pickling paste was rinsed off and the Heated weld seam with a sharp jet of water. The weld was bright and bare, the oxide layer completely removed and the base material free of one visible pickling attack.

    Claims (6)

    1. Aqueous pickling agent for special steels that is free of wetting agents and emulsifying agents and is based on sulphuric acid or phosphoric acid and hydrogen fluoride, characterised in that it contains (in each case in relation to 100 % by weight of substance)
      1.5 to 16 % by weight sulphuric acid or
      2.0 to 30 % by weight phosphoric acid
      and also
      0.5 to 14 % by weight hydrogen fluoride and
      0.5 to 15.5 % by weight acid-soluble aromatic nitro compound,
      to which no iron (III) compound is added and to which only in the initial phase an oxidizing agent oxidizing iron (II) to form iron (III) can be added.
    2. Pickling agent according to claim 1, characterised in that, when applied as a pickling bath, it contains
      5.0 to 11 % by weight sulphuric acid or
      8.0 to 20 % by weight phosphoric acid
      and also
      4.0 to 10 % by weight hydrogen fluoride and
      4.5 to 11 % by weight acid-soluble aromatic nitro
      compound.
    3. Pickling agent according to claim 1, characterised in that, when used as a pickle that is applied by spraying or with a brush, it additionally contains
      2.5 to 5.5 % by weight magnesium compound (calculated as Mg).
    4. Pickling agent according to claim 3,
      characterised in that, when used as a pickle that is applied by spraying, it contains
      9.5 to 15.5 % by weight sulphuric acid or
      15.0 to 30.0 % by weight phosphoric acid
      and also
      4.0 to 11.0 % by weight hydrogen fluoride,
      4.5 to 11.5 % by weight acid-soluble aromatic nitro compound and
      2.5 to 4.5 % by weight magnesium compound (calculated as Mg).
    5. Pickling agent according to claim 3,
      characterised in that, when used as a pickle that is applied with a brush, it contains
      12.0 to 16.0 % by weight sulphuric acid or
      18.0 to 30.0 % by weight phosphoric acid
      and also
      4.5 to 12.0 % by weight hydrogen fluoride,
      2.5 to 9.5 % by weight acid-soluble aromatic nitro compound and
      3.0 to 5.5 % by weight magnesium compound (calculated as Mg).
    6. Pickling agent according to one or more of claims 1 to 5, characterised in that it contains m-nitrobenzenesulphonate and/or 3-nitrophthalate as an acid-soluble aromatic nitro compound.
    EP99942796A 1998-07-29 1999-07-22 Stripper for special steel Expired - Lifetime EP1100982B1 (en)

    Applications Claiming Priority (3)

    Application Number Priority Date Filing Date Title
    DE19833990 1998-07-29
    DE19833990A DE19833990A1 (en) 1998-07-29 1998-07-29 Mordant for stainless steels
    PCT/EP1999/005226 WO2000006797A1 (en) 1998-07-29 1999-07-22 Stripper for special steel

    Publications (2)

    Publication Number Publication Date
    EP1100982A1 EP1100982A1 (en) 2001-05-23
    EP1100982B1 true EP1100982B1 (en) 2002-12-04

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    ID=7875604

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    Application Number Title Priority Date Filing Date
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    EP (1) EP1100982B1 (en)
    AT (1) ATE229098T1 (en)
    CA (1) CA2338484A1 (en)
    DE (2) DE19833990A1 (en)
    WO (1) WO2000006797A1 (en)

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    * Cited by examiner, † Cited by third party
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    DE10160318A1 (en) * 2001-12-07 2003-06-18 Henkel Kgaa Process for pickling martensitic or ferritic stainless steel
    DE102009038795A1 (en) * 2009-08-25 2011-05-05 Poligrat Gmbh Pickling process for stainless steel
    DE102013101629A1 (en) 2013-02-19 2014-08-21 Wolfgang DAMBACHER Apparatus and method for surface treatment of workpieces

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    CA2338484A1 (en) 2000-02-10
    US7041629B2 (en) 2006-05-09
    US20040053801A1 (en) 2004-03-18
    ATE229098T1 (en) 2002-12-15
    DE59903669D1 (en) 2003-01-16
    DE19833990A1 (en) 2000-02-10
    EP1100982A1 (en) 2001-05-23
    WO2000006797A1 (en) 2000-02-10

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