EP1100982A1 - Stripper for special steel - Google Patents

Stripper for special steel

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Publication number
EP1100982A1
EP1100982A1 EP99942796A EP99942796A EP1100982A1 EP 1100982 A1 EP1100982 A1 EP 1100982A1 EP 99942796 A EP99942796 A EP 99942796A EP 99942796 A EP99942796 A EP 99942796A EP 1100982 A1 EP1100982 A1 EP 1100982A1
Authority
EP
European Patent Office
Prior art keywords
weight
acid
pickling
hydrogen fluoride
compound
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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.)
Granted
Application number
EP99942796A
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German (de)
French (fr)
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EP1100982B1 (en
Inventor
Eckart SCHÖNFELDER
Günther Schwane
Harald Werner
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Chemetall GmbH
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Chemetall GmbH
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Publication of EP1100982A1 publication Critical patent/EP1100982A1/en
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Publication of EP1100982B1 publication Critical patent/EP1100982B1/en
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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
    • 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 emulsifier-free, aqueous pickling agent for stainless steel based on sulfuric acid or phosphoric acid and hydrogen fluoride.
  • pickling agents various acids or acid mixtures (pickling agents) in order to remove corrosion products and e.g. B. to remove scaling or tarnishing that has occurred during welding.
  • the pickling agent can be used as a bath pickle or - especially for large parts or local oxide formation - as a spray pickle or as a brush pickle.
  • the most important acids or acid mixtures for pickling stainless steels are hydrofluoric acid, hydrofluoric acid / nitric acid, hydrofluoric acid / sulfuric acid with some considerable additions of iron III compounds already in the starting phase of the pickling agent.
  • Some of the pickling agents contain hydrogen peroxide, with the help of which the iron II ions which go through the pickling attack in the solution are oxidized to iron III ions. 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.
  • the known pickling agents have various disadvantages.
  • the low pickling speed is often a disadvantage, and too high a pickling speed can also have a disadvantage if cycle times are specified in the pickling system. This applies in particular to hydrofluoric acid / nitric acid mordants.
  • these pickling agents with high acid concentrations, vapors which are hazardous to health emerge from the pickling baths and must be suctioned off and treated in a washing system. Because of the high solubility of the nitrates, it is also difficult to treat the rinsing water and waste water from the pickling process.
  • Sulfuric acid / hydrofluoric acid / hydrogen peroxide which are used in diving and for which it is generally necessary to maintain a certain redox potential, are comparatively complex in terms of process management, so that they are not considered, particularly for smaller pickling plants. Further disadvantages are that the hydrogen peroxide decomposes relatively easily in the mordant and with a low peroxide addition, only a slow oxide dissolution, ie low pickling rate, is obtained.
  • Another method consists in so-called degreasing and pickling iron-containing or consisting of objects. It works with solutions containing acids, wetting agents and / or emulsifiers as well as aromatic, water-soluble nitro compounds, such as e.g. Nitrobenzenesulfonate, contain (DE-A-25 07 059). Embadige degreasing and pickling inevitably leads to the entry of oils or fats in the pickling bath, as a result of which the pickling process is influenced in an incalculable manner. In particular, the formation of a uniform pickling pattern is prevented. The content of wetting agents and / or emulsifying agents also complicates the treatment of the rinsing and waste water obtained in the pickling process.
  • US Pat. No. 2,698,781 discloses a process known as a metal dissolver which uses aqueous strong acids containing an aromatic nitro compound. Taking the examples into account, this method is primarily intended for the treatment of nickel-plated copper as well as copper and lead. Only one example describes the pickling of stainless steels with a pickling bath containing sulfuric acid, m-nitro-benzenesulfonic acid and hydrofluoric acid, the sulfuric acid concentration being 200 g / l. Pickling baths with such a high sulfuric acid concentration, however, work comparatively slowly, so that the throughput is low.
  • the object of the invention is to provide an aqueous pickling agent for stainless steel which does not have the known, in particular the aforementioned disadvantages, and which is simple and inexpensive to carry out in terms of process.
  • the object is achieved by formulating the mordant of the type mentioned at the outset in accordance with the invention in such a way that (in each case as 100% by weight 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 wt .-% acid-soluble aromatic nitro compound, to which no iron III compound is supplied and which only oxidizes iron II to iron III in the starting phase Oxidizing agents can be added.
  • the pickling agent according to the invention used to carry out the pickling process can in principle also be used in the starting phase without iron II to oxidize oxidizing agent to iron III.
  • the pickling agent according to the invention can be used as a bath pickle, as a spray pickle or as a pickle pickle.
  • a mordant which, in its application as a bath stain, contains 5.0 to 11% by weight sulfuric acid or 8.0 to 20% by weight phosphoric acid and 4.0 to 10% by weight hydrogen fluoride and contains 4.5 to 11% by weight of 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 in terms of cost.
  • the pickling agent When used as a spray or pice pickle, the pickling agent preferably contains 2.5 to 5.5% by weight of magnesium compound (calculated as Mg).
  • the pickling agent is converted into em thixotropic gel by adding magnesium in the amounts mentioned. This ensures that a sufficient quantity of the pickling agent required for the pickling process is applied. It is particularly advantageous to add the magnesium in metallic form, as magnesium oxide, hydroxide, carbonate or sulfate.
  • a preferred embodiment of the invention provides that the mordant in its use as spray mordant 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 wt .-% acid-soluble aromatic nitro compound and 2.5 up to 4.5 wt .-% magnesium Veromdung (calculated as Mg) to use.
  • the mordant contains 12.0 to 16.0 wt.% Sulfuric acid or 18.0 to 30.0 wt. - Phosphoric acid and 4.5 to 12.0 Gev ⁇ . - i hydrogen fluoride, 2.5 to 9.5% by weight! acid-soluble aromatic nitro compound and 3.0 to 5.5% by weight; Magnesium v ⁇ rbm ⁇ ung (calculated as Mg).
  • Suitable acid-soluble aromatic nitro compounds are those which have at least one nitro and at least one acid group, in particular a carboxyl or sulfonic acid group, on the benzene ring. It is particularly advantageous to use m-nitrobenzenesulfonate and / or 3-nitrophthalate as the acid-soluble aromatic nitro compound.
  • the temperatures at which the mordants according to the invention are used vary depending on the type of application. When used as a bath stain, they are set to a value in the range of 15 to 80 ° C.
  • the pickling time is 5 to 90 mm, depending on the degree of scaling or oxide coating on the pickling material, the shorter pickling times for the higher pickling temperatures and the longer pickling times for the lower pickling temperatures.
  • the pickling temperatures are usually determined by the prevailing room or ambient temperatures. They are generally between 15 and 35 ° C.
  • the required pickling time is about 15 to 180 mm.
  • the pickling process is simple and inexpensive in terms of process feasible.
  • the desired and moderate pickling removal achieved with the pickling agent according to the invention light velvety surfaces are achieved.
  • the treatment of the winding and wastewater is easy because the
  • Calcium compounds can be precipitated and separated.
  • metal-pure sheets of stainless steel quality 1.4541 and 1.4462 were treated for one hour at 30 ° C in the mordant systems listed in the table below.
  • The% figures are to be understood as% by weight.
  • the plate pairs were spaced 2 minutes apart. optically checked for descaling of the weld seam and removal of tarnish.
  • the pair of sheets made of material 1.4511 was after 10 min., That of material 1.4462 after 24 min. clean.
  • the clear, viscous liquid obtained was sprayed onto steel grade 1.4301 sheets, which had a hand-drawn weld, with a pressure of 6 bar.
  • the obtained 1 to 2 mm thick film flowed not on vertical surfaces due to its thixotropy.
  • the spray stain was rinsed off.
  • the weld was descaled. The entire sheet surface was uniformly light and weakly stained.
  • the result was a non-flowable, opaque paste that was applied with a brush to the weld seam of a sheet of stainless steel quality 1.4571 with a thickness of 2 to 3 mm.
  • the pickling paste was rinsed off and the weld seam was sprayed off with a sharp water jet.
  • the weld seam was bright and bare, the oxide layer completely removed and the base material free of any visible pickling attack.

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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

Beizmittel für Edelstahle Pickling agent for stainless steel
Beschreibungdescription
Die Erfindung betrifft ein netz- und emulgiermittelfreies, wäßriges Beizmittel für Edelstahle auf Basis Schwefelsaure oder Phosphorsäure und Fluorwasserstoff.The invention relates to a wetting and emulsifier-free, aqueous pickling agent for stainless steel based on sulfuric acid or phosphoric acid and hydrogen fluoride.
Es ist allgemein üblich, Edelstahle mit verschiedenen Sauren oder Sauregemischen (Beizmitteln) zu beizen, um Korrosionsprodukte sowie z. B. beim Schweißen entstandene Zunderschichten oder Anlauffärben 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 pickle stainless steel with various acids or acid mixtures (pickling agents) in order to remove corrosion products and e.g. B. to remove scaling or tarnishing that has occurred during welding. The pickling agent can be used as a bath pickle or - especially for large parts or local oxide formation - as a spray pickle or as a brush pickle.
Die zum Beizen von Edelstahlen wichtigsten Säuren oder Sauregemische sind Flußsäure, Flußsaure/Salpetersaure, Flußsäure/Schwefelsäure mit zum Teil erheblichen Zus tzen an Eisen III-Verbιndungen bereits m der Startphase des Beizmitteis. Zum Teil enthalten die Beizmittel Wasserstoffperoxid, mit dessen Hilfe die durch den Beizangriff m Losung gehenden Eisen Il-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 or acid mixtures for pickling stainless steels are hydrofluoric acid, hydrofluoric acid / nitric acid, hydrofluoric acid / sulfuric acid with some considerable additions of iron III compounds already in the starting phase of the pickling agent. Some of the pickling agents contain hydrogen peroxide, with the help of which the iron II ions which go through the pickling attack in the solution are oxidized to iron III ions. 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 m Beizanlagen Taktzeiten vorgegeben sind. Dies gilt insbesondere f r Flußsaure/Salpetersaure -Beizmittel. Daruberhmaus treten bei diesen Beizmitteln mit hohen Saurekonzentrationen aus den Beizbadern gesundheitsgefahrdende Dampfe aus, die abgesaugt und in einer Waschanlage behandelt werden m ssen. Wegen der großen Loslichkeit der Nitrate ist zudem die Aufbereitung der im Beizprozeß anfallenden Spul- und Abwasser schwierig. Niedrig konzentrierte Beizmittel auf Basis Flußsaure/Salpetersaure sind zudem mit dem Nachteil behaftet, daß dunkle fleckige und nicht die an sich erwünschten metallisch hellen Metalloberflachen entstehen. Beizmittel, die zur Einstellung des erforderlichen Redoxpotentials bereits m der Startphase betrachtliche Zusätze von Fe III-Verbιndung 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.The known pickling agents have various disadvantages. The low pickling speed is often a disadvantage, and too high a pickling speed can also have a disadvantage if cycle times are specified in the pickling system. This applies in particular to hydrofluoric acid / nitric acid mordants. In addition, with these pickling agents with high acid concentrations, vapors which are hazardous to health emerge from the pickling baths and must be suctioned off and treated in a washing system. Because of the high solubility of the nitrates, it is also difficult to treat the rinsing water and waste water from the pickling process. Low-concentration pickling agents based on hydrofluoric acid / nitric acid also have the disadvantage that dark spotty and not the metallic light-colored metal surfaces that are desired per se are produced. Pickling agents, which already have considerable additions of Fe III compounds in the start phase to set the required redox potential, are deficient in that the absorption capacity of Fe II or Fe III originating from the oxide coating of the pickled material corresponds to the added Fe III - Quantity reduced.
Die Verfahren mit Beizmitteln auf BasisThe process with mordants based
Schwefelsaure/Flußsaure/Wasserstoffperoxid, die im Tauchen Anwendung finden und bei denen es m der Regel notig ist, ein bestimmtes Redox-Potential aufrechtzuerhalten, sind vergleichsweise aufwendig m der Verfahrensfuhrung, so daß sie insbesondere für kleinere Beizereien nicht m Betracht kommen. Weitere Nachteile sind, daß sich das Wasserstoffperoxid im Beizmittel relativ leicht zersetzt und bei geringem Peroxid-Zusatz eine nur langsame Oxidauflosung, d.h. geringe Beizgeschwindigkeit erhalten wird.Sulfuric acid / hydrofluoric acid / hydrogen peroxide, which are used in diving and for which it is generally necessary to maintain a certain redox potential, are comparatively complex in terms of process management, so that they are not considered, particularly for smaller pickling plants. Further disadvantages are that the hydrogen peroxide decomposes relatively easily in the mordant and with a low peroxide addition, only a slow oxide dissolution, ie low pickling rate, is obtained.
Ein weiteres Verfahren besteht in einem sogenannten embadigen Entfetten und Beizen von Eisen enthaltenden oder daraus bestehenden Gegenstanden. Es arbeitet mit Losungen, die Sauren, Netz-und/oder Emulgiermittel sowie als Oxidationsmittel aromatische, wasserlösliche Nitroverbmdungen, wie z.B. Nitrobenzolsulfonat, enthalten ( DE-A-25 07 059 ) . Das embadige Entfetten und Beizen fuhrt zwangsweise zum Eintrag von Ölen oder Fetten das Beizbad, wodurch der Beizprozeß m 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 Spul-und Abwasser.Another method consists in so-called degreasing and pickling iron-containing or consisting of objects. It works with solutions containing acids, wetting agents and / or emulsifiers as well as aromatic, water-soluble nitro compounds, such as e.g. Nitrobenzenesulfonate, contain (DE-A-25 07 059). Embadige degreasing and pickling inevitably leads to the entry of oils or fats in the pickling bath, as a result of which the pickling process is influenced in an incalculable manner. In particular, the formation of a uniform pickling pattern is prevented. The content of wetting agents and / or emulsifying agents also complicates the treatment of the rinsing and waste water obtained in the pickling process.
Schließlich ist aus der US-Patentschrift 2 698 781 ein als zum Auflosen von Metallen bezeichnetes Verfahren bekannt, das mit wäßrigen, eine aromatische Nitroverbindung enthaltenden starken Sauren arbeitet. Unter Berücksichtigung der Beispiele ist dieses Verfahren in erster Linie zur Behandlung von nickelplattiertem Kupfer sowie Kupfer und Blei bestimmt. Lediglich m einem Beispiel ist das Beizen von Edelstahlen mit einem Schwefelsaure, m-Nitro-Benzolsulfonsaure und Fluorwasserstoffsaure enthaltenden Beizbad beschrieben, wobei die Schwefelsaurekonzentration 200 g/1 betragt. Beizbader mit einer derartig hohen Schwefelsaurekonzentration arbeiten jedoch vergleichsweise langsam, so daß die Durchsatzleistung gering ist. Aufgabe der Erfindung ist, ein wäßriges Beizmittel für Edelstahle bereitzustellen, das die bekannten, insbesondere vorgenannten Nachteile, nicht aufweist, sowie verfahrensmaßig einfach und kostengünstig durchfuhrbar ist.Finally, US Pat. No. 2,698,781 discloses a process known as a metal dissolver which uses aqueous strong acids containing an aromatic nitro compound. Taking the examples into account, this method is primarily intended for the treatment of nickel-plated copper as well as copper and lead. Only one example describes the pickling of stainless steels with a pickling bath containing sulfuric acid, m-nitro-benzenesulfonic acid and hydrofluoric acid, the sulfuric acid concentration being 200 g / l. Pickling baths with such a high sulfuric acid concentration, however, work comparatively slowly, so that the throughput is low. The object of the invention is to provide an aqueous pickling agent for stainless steel which does not have the known, in particular the aforementioned disadvantages, and which is simple and inexpensive to carry out in terms of process.
Die Aufgabe wird gelost, indem das Beizmittel der eingangs genannten Art entsprechend der Erfindung derart formuliert wird, daß es (jeweils als 100 Gew.-%-ιge Substanz) 1,5 bis 16 Gew.-% Schwefelsaure oder 2,0 bis 30 Gew.-% Phosphorsaure sowie 0,5 bis 14 Gew.-% Fluorwasserstoff und 0,5 bis 15.5 Gew.-% saurelosliche aromatische Nitroverbindung enthalt, dem keine Eisen III-verbmdung zugeführt wird und dem lediglich m der Startphase Eisen II zu Eisen III oxidierendes Oxidationsmittel zugef hrt werden kann.The object is achieved by formulating the mordant of the type mentioned at the outset in accordance with the invention in such a way that (in each case as 100% by weight 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 wt .-% acid-soluble aromatic nitro compound, to which no iron III compound is supplied and which only oxidizes iron II to iron III in the starting phase Oxidizing agents can be added.
Das zur Durchfuhrung des Beizprozesses eingesetzte erfmdungsgemaße Beizmittel kann prinzipiell auch m 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 pickling agent according to the invention used to carry out the pickling process can in principle also be used in the starting phase without iron II to oxidize oxidizing agent to iron III. To activate the freshly prepared mordant, however, it may be advantageous to add small amounts of oxidizing agent, based on peroxide compounds, for example 0.05% by weight.
Das erfmdungsgemaße Beizmittel kann als Badbeize, als Sprüh- oder als P zelbeize zur Anwendung gelangen.The pickling agent according to the invention can be used as a bath pickle, as a spray pickle or as a pickle pickle.
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 01- 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, care must be taken that the pickling material can be completely wetted by the pickling agent. If 01 or grease residues on the pickling affect the complete wettability, prior cleaning is necessary or degreasing with the usual cleaners and a thorough water rinse before the pickling process.
Gemäß einer besonders bevorzugten Ausgestaltung der Erfindung gelangt em Beizmittel zum Einsatz, das m seiner Anwendung als Badbeize 5,0 bis 11 Gew.-% Schwefelsaure oder 8,0 bis 20 Gew.-% Phosphorsaure sowie 4,0 bis 10 Gew.- Fluorwasserstoff und 4,5 bis 11 Gew.-% saurelosliche aromatische Nitroverbindung enthalt.According to a particularly preferred embodiment of the invention, a mordant is used which, in its application as a bath stain, contains 5.0 to 11% by weight sulfuric acid or 8.0 to 20% by weight phosphoric acid and 4.0 to 10% by weight hydrogen fluoride and contains 4.5 to 11% by weight of acid-soluble aromatic nitro compound.
Das Beizmittel mit den vorgenannten Konzentrationsbereichen zeichnet sich durch eine hinreichend hohe Beizgeschwindigkeit aus, ohne daß das Grundmaterial angegriffen wird. Daruberhmaus ist es kostenmäßig besonders gjαnstig.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 in terms of cost.
Bei seiner Anwendung als Sprüh- oder P zelbeize enthalt des Beizmittel vorzugsweise 2,5 bis 5,5 Gew % Magnesiumverbindung ( ber. als Mg ) .When used as a spray or pice pickle, the pickling agent preferably contains 2.5 to 5.5% by weight of magnesium compound (calculated as Mg).
Durch Zugabe von Magnesium m den genannten Mengen wird das Beizmittel in em thixotropes Gel überfuhrt. Hierdurch wird der Auftrag einer ausreichenden Menge des für den Beizprozeß erforderlichen Beizmitteis gewährleistet. Besonders vorteilhaft ist es, das Magnesium m metallischer Form, als Magnesiumoxid, -hydroxid, -carbonat oder -sulfat zuzusetzen.The pickling agent is converted into em thixotropic gel by adding magnesium in the amounts mentioned. This ensures that a sufficient quantity of the pickling agent required for the pickling process is applied. It is particularly advantageous to add the magnesium in metallic form, as magnesium oxide, hydroxide, carbonate or sulfate.
Demzufolge sieht eine bevorzugte Ausgestaltung der Erfindung vor, das Beizmittel m seiner Anwendung als Spruhbeize mit einem Gehalt von 9,5 bis 15,5 Gew % Schwefelsaure oder 15,0 bis 30,0 Gew.-% Phosphorsaure, sowie 4,0 bis 11,0 Gew.-% Fluorwasserstoff, 4,5 bis 11,5 Gew.-% saurelosliche aromatische Nitroverbindung und 2,5 bis 4,5 Gew.-% Magnesiumveromdung (ber. als Mg) einzusetzen.Accordingly, a preferred embodiment of the invention provides that the mordant in its use as spray mordant 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 wt .-% acid-soluble aromatic nitro compound and 2.5 up to 4.5 wt .-% magnesium Veromdung (calculated as Mg) to use.
In einer weiteren bevorzugten Ausfuhrungsform der Erfindung enthalt das Beizmittel seiner Anwendung als Pinselbeize 12,0 b s 16,0 Gew o Schwefelsaure oder 18,0 bis 30.0 Gew . - Phosphorsaure sowie 4,5 bis 12,0 Gevι . - i Fluorwasserstoff, 2,5 bis 9,5 Gew.-! saurelosliche aromatische Nitroverbindung und 3,0 bis 5,5 Gew.-?; Magnesiumvεrbmαung (ber. als Mg) .In a further preferred embodiment of the invention, the mordant contains 12.0 to 16.0 wt.% Sulfuric acid or 18.0 to 30.0 wt. - Phosphoric acid and 4.5 to 12.0 Gevι. - i hydrogen fluoride, 2.5 to 9.5% by weight! acid-soluble aromatic nitro compound and 3.0 to 5.5% by weight; Magnesium vεrbmαung (calculated as Mg).
Geeignete saurelosliche aromatische Nitroverb αungen sind solche, die am Benzolring mindestens eine Nitro- und mindestens eine saure Gruppe, insbesondere eine Carboxyl- oder Sulfonsauregruppe aufweisen. Besonders vorteilhaft ist es, als saurelosliche aromatische Nitroverbindung m-Nitrobenzolsulfonat und/oder 3-Nιtrophthalat einzusetzen.Suitable acid-soluble aromatic nitro compounds are those which have at least one nitro and at least one acid group, in particular a carboxyl or sulfonic acid group, on the benzene ring. It is particularly advantageous to use m-nitrobenzenesulfonate and / or 3-nitrophthalate as the acid-soluble aromatic nitro compound.
Die Temperaturen, bei denen die erfmdungsgemaßen 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 betragt e nach Grad der Verzunderung bzw. Oxidbelag des Beizgutes 5 bis 90 mm., wobei die kürzeren Beizzeiten für die höheren Beiztemperaturen und die längeren Beizzeiten für die tieferen Beiztemperaturen gelten. Bei Anwendung des Beizmittels 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 betragt etwa 15 bis 180 mm.The temperatures at which the mordants according to the invention are used vary depending on the type of application. When used as a bath stain, they are set to a value in the range of 15 to 80 ° C. The pickling time is 5 to 90 mm, depending on the degree of scaling or oxide coating on the pickling material, the shorter pickling times for the higher pickling temperatures and the longer pickling times for the lower pickling temperatures. When using the pickling agent as a spray or brush stain, the pickling temperatures are usually determined by the prevailing room or ambient temperatures. They are generally between 15 and 35 ° C. The required pickling time is about 15 to 180 mm.
Mit Hilfe des erfmdungsgemaßen Beizmittels ist em verfahrensmaßig einfacher und kostengünstiger Beizprozeß durchfuhrbar. Infolge des angestrebten und mit den erfmdungsgemaßen Beizmittel erzielten maßigen Beizabtrages werden helle samtige Oberflachen erzielt. Die Aufbereitung der Spul- und Abwasser gestaltet sich einfach, da dieWith the aid of the pickling agent according to the invention, the pickling process is simple and inexpensive in terms of process feasible. As a result of the desired and moderate pickling removal achieved with the pickling agent according to the invention, light velvety surfaces are achieved. The treatment of the winding and wastewater is easy because the
Beizmittelkomponenten mit z.B. Kalkmilch als schwerlöslicheMordant components with e.g. Lime milk as poorly soluble
Calciumverbmdungen ausgefallt und abgetrennt werden können.Calcium compounds can be precipitated and separated.
Die Erfindung wird anhand der nachfolgenden Beispiele naher erläutertThe invention is explained in more detail with reference to the following examples
Beispiel 1example 1
Zur Ermittlung des Materialabtrages und der Oberflachenbeschaffenheit wurden metallisch reine Bleche der Edelstahlqualltaten 1.4541 und 1.4462 eine Stunde bei 30°C m den nachfolgend tabellarisch aufgeführten Beizmittelsystemen behandelt. Die %-Angaben verstehen sich als Gew.-%.In order to determine the material removal and the surface quality, metal-pure sheets of stainless steel quality 1.4541 and 1.4462 were treated for one hour at 30 ° C in the mordant systems listed in the table below. The% figures are to be understood as% by weight.
Die Ergebnisse sind hinsichtlich Materialabtrag m g/m2 in den Spalten zwei und drei, hinsichtlich Oberflachenbeschaffenheit m Spalte vier zusammengestellt. The results are summarized in columns two and three with regard to material removal mg / m 2 and column four with regard to surface quality.
Em Vergleich der Ergebnisse zeigt, daß - mit Ausnahme des Beizmitteis 4.) - allem die erfmdungsgemaßen Beizmittel 6.) und 7.) die erwünschte helle, samtige Oberflache entstehen ließen. Alle anderen führten zu leicht rauhen oder grauschwarz belegten, bzw. fleckigen Oberflachen. Dabei ist der Materialabtrag bei den Beizmitteln 6.) und 7.) vergleichsweise niedrig. Beispiel 2A comparison of the results shows that - with the exception of the pickling agent 4.) - all the pickling agents 6.) and 7.) according to the invention gave rise to the desired light, velvety surface. All others led to slightly rough or gray-black coated or stained surfaces. The material removal with the pickling agents 6.) and 7.) is comparatively low. Example 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 ausTwo 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 Gew.-% Fluorwasserstoff5 wt% hydrogen fluoride
7 Gew.-% Schwefelsäure und7% by weight sulfuric acid and
5,4 Gew.-% m-Nitrobenzolsulfonat5.4% by weight of m-nitrobenzenesulfonate
(eingebracht als Na-Salz)(introduced as Na salt)
Rest Wasser bestand.Remaining water existed.
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 checked for descaling of the weld seam and removal of tarnish.
Das Blechpaar aus den Material 1.4511 war nach 10 min., das aus dem Material 1.4462 nach 24 min. sauber.The pair of sheets made of material 1.4511 was after 10 min., That of material 1.4462 after 24 min. clean.
Beispiel 3Example 3
Es wurde eine Sprühbeize ausA spray stain was made
14 Gew.-% Schwefelsäure (96 Gew.-%)14% by weight sulfuric acid (96% by weight)
19 Gew.-% Flußsäure (50 Gew.-%)19% by weight hydrofluoric acid (50% by weight)
12,1 Gew.-% MgC03 und12.1 wt .-% MgC0 3 and
9 Gew.-% Na- m- Nitrobenzolsulfonat9% by weight of Na-nitrobenzenesulfonate
Rest Wasser formuliert .Formulated rest of water.
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 sprayed onto steel grade 1.4301 sheets, which had a hand-drawn weld, with a pressure of 6 bar. The obtained 1 to 2 mm thick film flowed not on vertical surfaces due to its thixotropy.
Nach einer Einwirkungszeit von lh wurde die Sprühbeize abgespült. Die Schweißnaht war sauber entzundert. Die gesamte Blechoberfläche war einheitlich hell und schwach angebeizt .After an exposure time of 1 h, the spray stain was rinsed off. The weld was descaled. The entire sheet surface was uniformly light and weakly stained.
Beispiel 4Example 4
Es wurde eine Pinselbeize ausThere was a brush stain
24 Gew.-% Phosphorsäure (85 Gew.-%)24% by weight phosphoric acid (85% by weight)
14 Gew.-% Flußsäure (70 Gew.-%)14% by weight of hydrofluoric acid (70% by weight)
6,6 Gew.-% Magnesiumoxid und6.6 wt .-% magnesium oxide and
5 Gew.-% 3-Nitrophthalsäure5% by weight of 3-nitrophthalic acid
Rest Wasser hergestellt .Rest of water made.
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.The result was a non-flowable, opaque paste that was applied with a brush to the weld seam of a sheet of stainless steel quality 1.4571 with a thickness of 2 to 3 mm.
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 weld seam was sprayed off with a sharp water jet. The weld seam was bright and bare, the oxide layer completely removed and the base material free of any visible pickling attack.

Claims

Patentansprüche claims
l.Netz- und emulgiermittelfreies wassriges Beizmittel für Edelstahle auf Basis Schwefelsaure oder Phosphorsaure und Fluorwasserstoff, dadurch gekennzeichnet, daß es (jeweils als 100 Gew.-%ιge Substanz)l.Wetting and emulsifier-free aqueous pickling agent for stainless steel based on sulfuric acid or phosphoric acid and hydrogen fluoride, characterized in that it (in each case as 100% by weight substance)
1,5 bis 16 Gew.-. Schwefelsaure oder1.5 to 16% by weight. Sulfuric acid or
2,0 bis 30 Gew.-% Phosphorsaure sowie2.0 to 30 wt .-% phosphoric acid as well
0,5 bis 14 Gew.-% Fluorwasserstoff und0.5 to 14 wt .-% hydrogen fluoride and
0,5 bis 15,5 Gew.-% saurelosliche aromatische0.5 to 15.5% by weight of acid-soluble aromatic
Nitroverbindung enthalt, dem keine Eisen III-Verbmdung zugeführt wird und dem lediglich m der Startphase Eisen II zu Eisen III oxidierendes Oxidationsmittel zugeführt werden kann.Contains nitro compound to which no iron III compound is supplied and which can only be supplied with an oxidizing agent which oxidizes iron II to iron III in the starting phase.
2. Beizmittel nach Anspruch 1, dadurch gekennzeichnet, daß es in seiner Anwendung als Badbeize2. Mordant according to claim 1, characterized in that it is used as a bath stain
5,0 bis 11 Gew.-% Schwefelsaure oder 8,0 bis 20 Gew.-% Phosphorsaure sowie5.0 to 11% by weight sulfuric acid or 8.0 to 20% by weight phosphoric acid as well
4,0 bis 10 Gew.-% Fluorwasserstoff und 4,5 bis 11 Gew.-% saurelosliche aromatische Nitroverbindung enthaltContains 4.0 to 10 wt .-% hydrogen fluoride and 4.5 to 11 wt .-% acid-soluble aromatic nitro compound
3. Beizmittel nach Anspruch 1, dadurch gekennzeichnet, daß es m seiner Anwendung als Spr h- oder Pinselbeize zusätzlich3. Mordant according to claim 1, characterized in that it additionally m its application as a spray or brush stain
2,5 bis 5,5 Gew.- Magnesiumverbindung2.5 to 5.5 parts by weight of magnesium compound
(ber. als Mg) enthalt. (calculated as Mg).
4. Beizmittel nach den Ansprüchen 1 und 3, dadurch gekennzeichnet, daß es in seiner Anwendung als Sprühbeize4. Mordant according to claims 1 and 3, characterized in that it is used as a spray stain
9,5 bis 15,5 Gew.-% Schwefelsäure oder 15,0 bis 30,0 Gew.-% Phosphorsäure sowie9.5 to 15.5% by weight of sulfuric acid or 15.0 to 30.0% by weight of phosphoric acid as well
4,0 bis 11,0 Gew.-% Fluorwasserstoff,4.0 to 11.0% by weight of hydrogen fluoride,
4,5 bis 11,5 Gew.- säurelösliche aromatische4.5 to 11.5% by weight acid-soluble aromatic
Nitroverbindung und 2,5 bis 4,5 Gew.-% Magnesiumverbindung (ber. als Mg) enthält .Contains nitro compound and 2.5 to 4.5 wt .-% magnesium compound (calc. As Mg).
5. Beizmittel nach den Ansprüchen 1 und 3, dadurch gekennzeichnet, daß es in seiner Anwendung als Pinselbeize5. Mordant according to claims 1 and 3, characterized in that it is used as a brush stain
12,0 bis 16,0 Gew.-% Schwefelsäure oder 18,0 bis 30,0 Gew.-% Phosphorsäure sowie12.0 to 16.0% by weight of sulfuric acid or 18.0 to 30.0% by weight of phosphoric acid as well
4,5 bis 12,0 Gew.-% Fluorwasserstoff,4.5 to 12.0% by weight of hydrogen fluoride,
2,5 bis 9,5 Gew.-% säurelösliche aromatische2.5 to 9.5% by weight of acid-soluble aromatic
Nitroverbindung und 3,0 bis 5,5 Gew.-% Magnesiumverbindung (ber. als Mg) enthältContains nitro compound and 3.0 to 5.5 wt .-% magnesium compound (calc. As Mg)
6. Beizmittel nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß es als säurelösliche aromatische Nitroverbindung m-Nitrobenzolsulfonat und/oder 3-Nitrophthalat enthält. 6. Mordant according to one or more of claims 1 to 5, characterized in that it contains m-nitrobenzenesulfonate and / or 3-nitrophthalate as the acid-soluble aromatic nitro compound.
EP99942796A 1998-07-29 1999-07-22 Stripper for special steel Expired - Lifetime EP1100982B1 (en)

Applications Claiming Priority (3)

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

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EP1100982B1 EP1100982B1 (en) 2002-12-04

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DE102013101629A1 (en) 2013-02-19 2014-08-21 Wolfgang DAMBACHER Apparatus and method for surface treatment of workpieces

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DE19833990A1 (en) 2000-02-10
US7041629B2 (en) 2006-05-09
WO2000006797A1 (en) 2000-02-10
ATE229098T1 (en) 2002-12-15
US20040053801A1 (en) 2004-03-18

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