WO2000006797A1 - Beizmittel für edelstähle - Google Patents
Beizmittel für edelstähle Download PDFInfo
- Publication number
- WO2000006797A1 WO2000006797A1 PCT/EP1999/005226 EP9905226W WO0006797A1 WO 2000006797 A1 WO2000006797 A1 WO 2000006797A1 EP 9905226 W EP9905226 W EP 9905226W WO 0006797 A1 WO0006797 A1 WO 0006797A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- weight
- acid
- pickling
- sulfuric acid
- soluble aromatic
- Prior art date
Links
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.
Landscapes
- 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
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002338484A CA2338484A1 (en) | 1998-07-29 | 1999-07-22 | Stripper for special steel |
AT99942796T ATE229098T1 (de) | 1998-07-29 | 1999-07-22 | Beizmittel für edelstähle |
EP99942796A EP1100982B1 (de) | 1998-07-29 | 1999-07-22 | Beizmittel für edelstähle |
DE59903669T DE59903669D1 (de) | 1998-07-29 | 1999-07-22 | Beizmittel für edelstähle |
US10/648,658 US7041629B2 (en) | 1998-07-29 | 2003-08-26 | Stripper for special steel |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19833990.9 | 1998-07-29 | ||
DE19833990A DE19833990A1 (de) | 1998-07-29 | 1998-07-29 | Beizmittel für Edelstähle |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09743396 A-371-Of-International | 2001-03-29 | ||
US10/648,658 Continuation US7041629B2 (en) | 1998-07-29 | 2003-08-26 | Stripper for special steel |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000006797A1 true WO2000006797A1 (de) | 2000-02-10 |
Family
ID=7875604
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1999/005226 WO2000006797A1 (de) | 1998-07-29 | 1999-07-22 | Beizmittel für edelstähle |
Country Status (6)
Country | Link |
---|---|
US (1) | US7041629B2 (de) |
EP (1) | EP1100982B1 (de) |
AT (1) | ATE229098T1 (de) |
CA (1) | CA2338484A1 (de) |
DE (2) | DE19833990A1 (de) |
WO (1) | WO2000006797A1 (de) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10160318A1 (de) * | 2001-12-07 | 2003-06-18 | Henkel Kgaa | Verfahren zum Beizen von martensitischem oder ferritischem Edelstahl |
DE102009038795A1 (de) * | 2009-08-25 | 2011-05-05 | Poligrat Gmbh | Beizverfahren für Edelstahl |
DE102013101629A1 (de) | 2013-02-19 | 2014-08-21 | Wolfgang DAMBACHER | Vorrichtung und Verfahren zur Oberflächenbehandlung von Werkstücken |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2698781A (en) * | 1953-04-27 | 1955-01-04 | Enthone | Accelerating action of acids on metals |
US3239467A (en) * | 1962-02-15 | 1966-03-08 | Lord Corp | Metal cleaning and treating compositions |
DE1950560A1 (de) * | 1968-10-07 | 1970-04-23 | Chugai Kasei Co Ltd | Reinigungs- und AEtzmittel fuer Metalloberflaechen |
DE2507059A1 (de) * | 1975-02-19 | 1976-09-02 | Basf Ag | Verfahren zur reinigung von eisen enthaltenden metallgegenstaenden |
JPS5610396A (en) * | 1979-07-07 | 1981-02-02 | Nobuo Miyazawa | Additive for acid bath for descaling of stainless steel |
EP0058257A1 (de) * | 1981-02-14 | 1982-08-25 | Metallgesellschaft Ag | Beiz- und Entrostungspaste für Metalle |
FR2520374A1 (fr) * | 1982-01-22 | 1983-07-29 | Enthone | Compositions et procede pour l'elimination chimique selective de revetements superficiels durs de substrats en superalliage |
DE3530132A1 (de) * | 1985-08-23 | 1987-02-26 | August Wittig | Oberflaechen beiz- und entrostungspaste zum reinigen von metalloberflaechen insbesondere aus edelstahl und/oder aluminium u. aluminiumlegierungen |
DE4237021C1 (de) * | 1992-11-02 | 1994-02-10 | Poligrat Gmbh | Mittel zum Beizen der Oberfläche von Chromnickelstählen und Chromstählen sowie Verwendung des Mittels |
WO1995035397A1 (en) * | 1994-06-17 | 1995-12-28 | Ta Chemistry Ab | Process for stainless steel pickling |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2339467A (en) * | 1942-02-13 | 1944-01-18 | Hoe & Co R | Mechanism for registering printing plates |
US4971631A (en) * | 1988-03-07 | 1990-11-20 | Bernard Lietaer | Compositions and methods for cleaning hard surfaces |
FR2657888B1 (fr) * | 1990-02-08 | 1994-04-15 | Ugine Aciers | Procedes de decapage de materiaux en acier inoxydable. |
FR2673200A1 (fr) * | 1991-02-25 | 1992-08-28 | Ugine Aciers | Procede de surdecapage de materiaux en acier tels que les aciers inoxydables et les aciers allies. |
FR2683551B1 (fr) * | 1991-11-07 | 1994-09-16 | Ugine Sa | Procede de decapage de materiaux en acier en continu sur une ligne de traitement. |
FR2721328B1 (fr) * | 1994-06-15 | 1996-09-06 | Ugine Sa | Procédé de décapage de matériaux métalliques, notamment en acier allié, en acier inoxydable ou en alliage de titane, par une solution du type contenant des ions ferriques en milieu acide. |
US5711996A (en) * | 1995-09-28 | 1998-01-27 | Man-Gill Chemical Company | Aqueous coating compositions and coated metal surfaces |
US5702534A (en) * | 1996-05-24 | 1997-12-30 | Armco Inc. | Hydrogen peroxide pickling of stainless steel |
-
1998
- 1998-07-29 DE DE19833990A patent/DE19833990A1/de not_active Withdrawn
-
1999
- 1999-07-22 WO PCT/EP1999/005226 patent/WO2000006797A1/de active IP Right Grant
- 1999-07-22 DE DE59903669T patent/DE59903669D1/de not_active Expired - Lifetime
- 1999-07-22 EP EP99942796A patent/EP1100982B1/de not_active Expired - Lifetime
- 1999-07-22 AT AT99942796T patent/ATE229098T1/de not_active IP Right Cessation
- 1999-07-22 CA CA002338484A patent/CA2338484A1/en not_active Abandoned
-
2003
- 2003-08-26 US US10/648,658 patent/US7041629B2/en not_active Expired - Fee Related
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2698781A (en) * | 1953-04-27 | 1955-01-04 | Enthone | Accelerating action of acids on metals |
US3239467A (en) * | 1962-02-15 | 1966-03-08 | Lord Corp | Metal cleaning and treating compositions |
DE1950560A1 (de) * | 1968-10-07 | 1970-04-23 | Chugai Kasei Co Ltd | Reinigungs- und AEtzmittel fuer Metalloberflaechen |
DE2507059A1 (de) * | 1975-02-19 | 1976-09-02 | Basf Ag | Verfahren zur reinigung von eisen enthaltenden metallgegenstaenden |
JPS5610396A (en) * | 1979-07-07 | 1981-02-02 | Nobuo Miyazawa | Additive for acid bath for descaling of stainless steel |
EP0058257A1 (de) * | 1981-02-14 | 1982-08-25 | Metallgesellschaft Ag | Beiz- und Entrostungspaste für Metalle |
FR2520374A1 (fr) * | 1982-01-22 | 1983-07-29 | Enthone | Compositions et procede pour l'elimination chimique selective de revetements superficiels durs de substrats en superalliage |
DE3530132A1 (de) * | 1985-08-23 | 1987-02-26 | August Wittig | Oberflaechen beiz- und entrostungspaste zum reinigen von metalloberflaechen insbesondere aus edelstahl und/oder aluminium u. aluminiumlegierungen |
DE4237021C1 (de) * | 1992-11-02 | 1994-02-10 | Poligrat Gmbh | Mittel zum Beizen der Oberfläche von Chromnickelstählen und Chromstählen sowie Verwendung des Mittels |
WO1995035397A1 (en) * | 1994-06-17 | 1995-12-28 | Ta Chemistry Ab | Process for stainless steel pickling |
Non-Patent Citations (1)
Title |
---|
PATENT ABSTRACTS OF JAPAN vol. 005, no. 058 (C - 051) 21 April 1981 (1981-04-21) * |
Also Published As
Publication number | Publication date |
---|---|
EP1100982B1 (de) | 2002-12-04 |
DE59903669D1 (de) | 2003-01-16 |
CA2338484A1 (en) | 2000-02-10 |
ATE229098T1 (de) | 2002-12-15 |
US7041629B2 (en) | 2006-05-09 |
DE19833990A1 (de) | 2000-02-10 |
US20040053801A1 (en) | 2004-03-18 |
EP1100982A1 (de) | 2001-05-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE2054067C3 (de) | Mittel zum Reinigen von Aluminiumoberflächen, zum Desoxydieren, Reinigen und Einebnen bzw. zur Glanzgebung von Oberflächen aus rostfreiem Stahl und zum Bilden eines Eisenphosphatüberzugs auf eisenhaltigen Oberflächen | |
DE2359021A1 (de) | Beizloesung und verfahren zum beizen von metallen | |
DE2711429A1 (de) | Verfahren zur reinigung von zinn- oberflaechen | |
DE68919033T2 (de) | Reinigungsverfahren für Metalle. | |
DE69203430T2 (de) | Entfettungslösung und deren Verfahren. | |
DE3706711A1 (de) | Verfahren zum reinigen von oberflaechen eines aluminiumgegenstandes | |
DE2845736A1 (de) | Verfahren zur galvanischen abscheidung eines bronzebelags auf aluminium | |
DE2758629C3 (de) | Verfahren zum Reinigen der verzinnten Oberfläche eines eisenhaltigen Metalls | |
DE2531163C2 (de) | Verfahren zur Verbesserung der Lötbarkeit elektrischer Leiterplatten | |
DE3925169A1 (de) | Verfahren zur nachbehandlung von elektroplattierten, zum verloeten vorgesehenen stahlblechen | |
DE4237021C1 (de) | Mittel zum Beizen der Oberfläche von Chromnickelstählen und Chromstählen sowie Verwendung des Mittels | |
DE102005037563B3 (de) | Elektropolierverfahren | |
EP1100982B1 (de) | Beizmittel für edelstähle | |
DE2923068A1 (de) | Verfahren zur metalloberflaechenbehandlung | |
DE1521888A1 (de) | Verfahren,Loesung und Konzentrat zum Reinigen von metallischen Oberflaechen und zur Bildung eines Phosphatueberzuges | |
DE4417284C2 (de) | Verfahren zum Beizen von Werkstücken aus hochlegierten Werkstoffen | |
DE102020106543A1 (de) | Verfahren zum Verzinken eines Bauteils, insbesondere für ein Kraftfahrzeug, sowie Bauteil für ein Kraftfahrzeug | |
DE3217145A1 (de) | Verfahren zum reinigen, entfetten sowie aktivieren von metalloberflaechen | |
DE885333C (de) | Verfahren zur elektrochemischen Behandlung von Metallkoerpern zwecks Abtragens von Oberflaechenschichten | |
DE2041871B2 (de) | Verfahren zur Vorbehandlung von Rost aufweisenden, eisenhaltigen Oberflächen für die elektrophoretische Lackierung | |
EP1022357B1 (de) | Verfahren zur Oberflächenbehandlung von rostfreien Stählen | |
DE2014782A1 (de) | Reinigungsmittel für Metalloberflächen | |
DE1621611A1 (de) | Verfahren und Loesung zum Beizen von Kupferlegierungen | |
DE913977C (de) | Emaillierverfahren | |
DE1202615B (de) |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): CA MX SG US |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 1999942796 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 2338484 Country of ref document: CA Ref country code: CA Ref document number: 2338484 Kind code of ref document: A Format of ref document f/p: F |
|
WWE | Wipo information: entry into national phase |
Ref document number: 09743396 Country of ref document: US |
|
WWP | Wipo information: published in national office |
Ref document number: 1999942796 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: CA |
|
WWG | Wipo information: grant in national office |
Ref document number: 1999942796 Country of ref document: EP |