EP2352860A1 - Verfahren zur oberflächenbehandlung von nichtrostendem stahl - Google Patents
Verfahren zur oberflächenbehandlung von nichtrostendem stahlInfo
- Publication number
- EP2352860A1 EP2352860A1 EP09737363A EP09737363A EP2352860A1 EP 2352860 A1 EP2352860 A1 EP 2352860A1 EP 09737363 A EP09737363 A EP 09737363A EP 09737363 A EP09737363 A EP 09737363A EP 2352860 A1 EP2352860 A1 EP 2352860A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- salt
- oxide layers
- acid
- stainless steel
- thermal oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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
- C23G1/088—Iron or steel solutions containing organic acids
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/50—Treatment of iron or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- C23G1/28—Cleaning or pickling metallic material with solutions or molten salts with molten salts
- C23G1/32—Heavy metals
Definitions
- the present invention relates to a process for surface treatment of stainless steel instead of pickling.
- scale and tarnish in the area of welds and heat-treated surfaces are converted into corrosion-resistant oxide layers.
- the aim of this process is improved corrosion resistance without metal removal taking place.
- the stainless steel surface is treated with an aqueous or pasty solution / mixture.
- the mixture usually comprises a combination of complexing agents and an oxidizing agent.
- Stainless steel which is also often referred to as stainless steel, is an iron alloy which, in addition to iron and chromium, may also contain other elements such as nickel, molybdenum, titanium, copper and others.
- An essential component of the stainless steel alloys whose treatment is the subject of the present invention is the element chromium, which is present in a minimum concentration of about 12 wt .-%, in order to ensure increased resistance of the steel to corrosion.
- the chromium present in the alloy reacts with oxygen from the environment at the surface to form an oxide layer on the surface of the material.
- the resulting chromium oxide can reliably form a dense layer on the surface and thus protects the workpiece from corrosion.
- This protective layer is called a passive layer.
- Such a passive layer is usually about 10 molecule layers thick and contains not only chromium oxide but above all iron oxide in a concentration of 10 - 55 wt .-%. The lower the proportion of iron oxide in the passive layer, the higher its chemical resistance.
- a thermal treatment of stainless steel in an oxidizing atmosphere at temperatures above 200 0 C causes a progressive thermal oxidation of the material to form an oxide layer consisting essentially of oxides of in
- the thermal oxide layers therefore contain up to about 87% by weight of iron oxides. These oxide layers increase in thickness with increasing temperature and treatment time and lead to discoloration up to black or gray lo coverings. These are known as tinder and temper colors.
- Such oxide layers which contain significantly more iron oxide than chromium oxide, are not resistant to corrosion, which is why the stainless steel in these areas is not sufficiently resistant to corrosion for general use.
- the iron oxide reacts with water to form iron hydroxide and forms rust.
- Electrolytic pickling uses aqueous mixtures of mineral acids, which lead under the action of direct current to anodic removal of the top metal layer 0 by electrochemical dissolution, wherein the overlying oxide layers are eliminated with. These methods can only be used with thin oxide layers that are permeable to DC and electrolyte. Furthermore, they require a lot of effort in terms of plant technology. They work with hazardous substances, which also produce wastewater containing heavy metals, which requires extensive treatment and disposal. Chemical pickling chemically dissolves the oxide layers and the metal of the topmost material layer, creating a metallically clean surface. On top of this, a homogeneous passive layer can be formed which effectively protects the material from corrosion. Chemical pickling allows the entire surface of workpieces to be treated, including hard-to-reach areas. A disadvantage is the fact that the dissolution of the oxides and the material extremely aggressive and hazardous chemicals are required, which pose a high risk to humans and the environment.
- hydrofluoric acid or fluorides of salts of hydrofluoric acid, which form hydrofluoric acid in aqueous solution, as well as oxidants such as nitric acid or hydrogen peroxide.
- Hydrofluoric acid is extremely poisonous and can lead to death even with relatively little skin contact. Nitric acid releases toxic nitrous gases during pickling, which have a strong lung damaging effect.
- Hydrofluoric acid and nitric acid are gaseous acids, which is why the air in the working environment has to be sucked off and treated separately.
- the personnel employed for chemical pickling must wear appropriate protective clothing and, where appropriate, respiratory protection and is subject to constant medical supervision.
- the manufacture, transportation, storage and use of chemicals used for chemical pickling are subject to strict safety regulations.
- the wastewater produced by chemical pickling contains in a high concentration the acids contained in the pickle as well as the heavy metals contained in the alloy such as chromium, iron, nickel and molybdenum. They must be chemically treated with care for disposal 5 and the resulting solids should be dumped as hazardous waste. Used pickling solutions are to be disposed of as hazardous waste.
- the present invention is a chemical process for the treatment of the surface of stainless steel, harmless to humans and the environment and respectable 5 let the achievable corrosion resistance of the method according to the prior art at least equivalent, but in many cases clearly superior.
- the present invention selects a new, previously unused path to solve the problem:
- the invention is based on the idea that it is basically not necessary to eliminate the existing thermal oxide layers. Instead, it is also sufficient to reduce the concentration of iron oxides in the thermal oxide layers so far that the thermal oxide layers result in a concentration ratio of chromium oxides to iron oxides, which corresponds at least to that of intact passive layers.
- an agent is needed whose chemical affinity is more selective to iron than the affinity of iron for oxygen. This makes it possible that the iron oxides are split. The iron can then be selectively removed from the thermal oxide layers.
- an aqueous solution with a special combination of organic complexing agents in combination with an oxidizing agent has these sought-after properties.
- the process according to the invention makes it possible selectively to remove the iron from all oxidation states of the iron, with the exception of hematite.
- hematite is chemically sufficiently stable even under corrosive conditions so that residual hematite residues have no negative impact on the corrosion resistance of stainless steel.
- the invention thus provides a process for surface treatment of stainless steel, in which the thermal oxide layers are brought into contact with a composition which causes a selective dissolution of iron ions from the oxide layer.
- the surfaces which are treated according to the invention are stainless steel surfaces which have so-called thermal oxide layers.
- Thermal oxide layers are just not such oxide-containing layers that usually serve to passivate the stainless steel surface. Rather, the thermal oxide layers are unwanted and disruptive oxide layers which, on the one hand, lead to discoloration and, on the other hand, are themselves susceptible to corrosion or increase the susceptibility to corrosion of a stainless steel surface. Therefore, it is always necessary according to the state of the art that thermal oxide layers are removed in the context of corrosion resistance-improving measures.
- the present invention differs not only conceptually but also fundamentally from the prior art with regard to the aqueous solution actually used. Namely, according to the prior art, there is a pickling, ie ablation, treatment of the stainless steel surface, with the result that the thermal oxide layers are completely removed.
- a pickling, ie ablation, treatment of the stainless steel surface with the result that the thermal oxide layers are completely removed.
- Such a method is described for example in the utility model DE 92 14 890 U1 of the applicant in which the stainless steel surfaces are treated with a solution containing phosphoric acid and sulfuric acid in an erosive manner until neither scale residues nor discoloration around a weld seam can be observed.
- Thermal oxide layers according to the invention are scale and tarnish, as they usually occur during thermal treatment or when welding stainless stainless steel. These surface layers are regularly recognized by the fact that they lead to a discoloration of the surface. The surface may then have a straw-yellow coloration, but may, depending on the duration and intensity of the thermal treatment of the surface, even in brown and blue shades.
- the method according to the invention thus acts in a similar way to a pickling method, in which, unlike pickling according to the prior art, the thermal oxide layers are not detached. Therefore, it is also possible according to the invention to use such mixtures which do not entail the disadvantages of the pickling baths used in the prior art.
- the dissolution of the iron ions from the surface preferably takes place selectively.
- selective herein is meant that the complexing agent has a stronger affinity (i.e., greater complexing) to the iron than to the other components in the thermal oxide layers (eg, chromium or nickel).
- the solutions / mixtures according to the invention comprise a combination of a complexing agent for iron and an oxidizing agent.
- the complexing agent is usually such a compound that can complex iron ions in aqueous solution.
- hydroxycarboxylic acids, phosphonic acids and organic nitrosulfonic acids can be used as complexing agents.
- the preferred complexing agents are multidentate complexing agents. These multimetallic complexing agents can form chelate complexes with iron ions. This makes it possible to increase the ratio of chromium oxide to iron oxide in the thermal oxide layers.
- suitable complexing agents furthermore include hydroxycarboxylic acids which have 1, 2 or 3 hydroxyl groups and 1, 2 or 3 carboxyl groups or their salts.
- a particularly suitable hydroxycarboxylic acid is citric acid.
- Another suitable complexing agent is the phosphonic acid having the general formula R'-PO (OH) 2 , where R 'is a monovalent alkyl, hydroxyalkyl or aminoalkyl radical.
- Diphosphonic acid of the general formula R "[- PO (OH) 2 ] 2 can also be used according to the invention, where R" is a divalent alkyl, hydroxyalkyl or aminoalkyl radical. Instead of or in addition to these phosphonic acids and / or
- Diphosphonic acids can also be used one or more salts of these phosphonic acids or diphosphonic acids.
- a particularly preferred example of such an acid is 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or its salt.
- Further suitable complexing agents are the organic nitrosulfonic acids, for example nitroalkylsulfonic acids, nitroarylsulfonic acids or salts thereof.
- a particularly preferred nitroarylsulfonic acid is the meta-nitrobenzenesulfonic acid.
- the substituted or unsubstituted alkyl or aryl radicals used should be selected such that the acid or salt has sufficient solubility in the aqueous solution / mixture. Therefore, a hydrocarbon chain preferably has not more than twelve carbon atoms.
- compositions of the invention may additionally contain oxidizing agents.
- Suitable oxidizing agents are, for example, nitrates, peroxo compounds, iodates and cerium (IV) compounds in the form of the respective acids or of the water-soluble salts.
- peroxo compounds are peroxides, persulfates, perborates or else percarboxylates, such as peracetate.
- the oxidizing agents may be used alone or in the form of mixtures.
- an iron alloy containing a considerable proportion for example, about 13 wt .-% and more chromium.
- the solutions / mixtures according to the invention may additionally comprise one or more wetting agents which reduce the surface tension of the aqueous compositions.
- suitable wetting agents are, for example, the nitroalkyl- or nitroarylsulfonic acids already described in connection with complexing agents, or also alkylglycols of the general formula H- (O-CHR-CH 2 ) n -OH, where R is hydrogen or an alkyl radical with 1 , 2 or 3 carbon atoms, and n is preferably an integer between 1 and 5, for example 2 or 3.
- a particularly suitable composition which can be used for the surface treatment according to the invention has the following composition:
- compositions may optionally contain one or more thickening agents.
- suitable thickeners are, for example, methyl cellulose and kieselguhr. Such a thickener serves to increase the viscosity of the mixture.
- the inventive method is carried out regularly at a temperature between room temperature and 95 0 C. But there are also other temperatures conceivable, while it must always be ensured that there is no significant removal of the treated thermal oxide layers.
- the surface treatment according to the invention is usually carried out over a period of time which can be between 0.5 and 7 hours.
- the stainless steel surface is periodically rinsed with water, usually with deionized water rinse.
- the pickling process can be carried out as a liquid by spraying, trickling, wiping or - slightly thickened by a suitable thickener (methylcellulose) - as spreadable paste in the dipping bath or by applying to the surfaces to be cleaned.
- a suitable thickener methylcellulose
- the application temperature is in the immersion bath is preferably 50 0 C to 95 0 C, preferably from 50 0 C to 70 0 C.
- the treatment time is 3 to 5 hours depending on the degree of scaling, the alloy to be treated and the temperature employed. At lower temperatures, the exposure time may be longer. Temperatures below 50 ° C are only used in applications outside the bath. The temperature of the baths should be at least 50 0 C permanently, to prevent biological degradation of the bath liquid.
- the present invention therefore also relates to the use of a complexing agent for iron-containing composition, which in essence is free of hydrofluoric acid and / or of fluoride ions and other halide ions and mineral acids, for the surface treatment of a workpiece made of stainless steel, said surface having thermal oxide layers.
- the other constituents of the composition and the procedure for the surface treatment the prerequisites and features previously established and specified for the method apply.
- the phrase "substantially free of hydrofluoric acid and / or fluoride ions” means that the composition does not contain hydrofluoric acid in an amount present in conventional mordants, but preferably the composition is completely free of hydrofluoric acid no mineral acids.
- Sample B was immersed in a pickling solution consisting of 5% by weight of hydrofluoric acid and 15% by weight of nitric acid, the remainder water, for 3 hours at room temperature, then rinsed with deionized water and allowed to stand for 30 minutes Room temperature in a passivation solution consisting of 20 wt .-% nitric acid, balance water, immersed. Finally, the sample was rinsed with deionized water and dried.
- Sample C was composed of a solution
- citric acid 2.1% nitroalkylsulfonic acid 3.5% hydroxyethanediphosphonic acid 0.2% ethylene glycol
- the pitting potential against an Ag / AgCl electrode in millivolts was then measured potentiodynamically on samples A, B and C in an artificial seawater containing 20,000 ppm of chloride.
- the measurement was carried out at three points in the area of the blank, non-heat-affected area, in the area of the meeinflußzone and in the region of the weld. The results are shown in table.
- the method according to the invention can be used everywhere and does not require special protective measures for humans and the environment.
- the method according to the invention selectively dissolves iron exclusively from the already existing thermal oxide layer. Chromium, nickel, molybdenum and others
- the method according to the invention does not attack the metal of the workpiece surface, which is why the appearance and quality of the surfaces do not suffer from the treatment.
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)
- Chemical Treatment Of Metals (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP09737363.3A EP2352860B1 (de) | 2008-10-29 | 2009-10-15 | Verfahren zur oberflächenbehandlung von nichtrostendem stahl |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP08018874A EP2182095A1 (de) | 2008-10-29 | 2008-10-29 | Verfahren zur Oberflächenbehandlung von nichtrostendem Stahl |
PCT/EP2009/007402 WO2010049065A1 (de) | 2008-10-29 | 2009-10-15 | Verfahren zur oberflächenbehandlung von nichtrostendem stahl |
EP09737363.3A EP2352860B1 (de) | 2008-10-29 | 2009-10-15 | Verfahren zur oberflächenbehandlung von nichtrostendem stahl |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2352860A1 true EP2352860A1 (de) | 2011-08-10 |
EP2352860B1 EP2352860B1 (de) | 2015-12-16 |
Family
ID=40451451
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP08018874A Withdrawn EP2182095A1 (de) | 2008-10-29 | 2008-10-29 | Verfahren zur Oberflächenbehandlung von nichtrostendem Stahl |
EP09737363.3A Not-in-force EP2352860B1 (de) | 2008-10-29 | 2009-10-15 | Verfahren zur oberflächenbehandlung von nichtrostendem stahl |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP08018874A Withdrawn EP2182095A1 (de) | 2008-10-29 | 2008-10-29 | Verfahren zur Oberflächenbehandlung von nichtrostendem Stahl |
Country Status (8)
Country | Link |
---|---|
US (1) | US9115433B2 (de) |
EP (2) | EP2182095A1 (de) |
JP (1) | JP5586614B2 (de) |
AU (1) | AU2009310094A1 (de) |
CA (1) | CA2741704A1 (de) |
ES (1) | ES2559387T3 (de) |
HU (1) | HUE026531T2 (de) |
WO (1) | WO2010049065A1 (de) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105849312A (zh) * | 2013-12-18 | 2016-08-10 | 波里格拉特股份有限公司 | 有色不锈钢表面的生产方法 |
JP6526406B2 (ja) * | 2014-12-10 | 2019-06-05 | 株式会社Ihi | ステンレス鋼部品の不動態化処理方法及びステンレス鋼部品用の不動態化処理液 |
DK3249076T3 (en) | 2016-05-24 | 2018-11-26 | Technochim Sa | Stainless steel preventive treatment products and related methods |
US10443135B1 (en) * | 2018-05-11 | 2019-10-15 | Macdermid Enthone Inc. | Near neutral pH pickle on multi-metals |
JP6592624B2 (ja) * | 2019-01-15 | 2019-10-16 | 株式会社Ihi | ステンレス鋼部品の不動態化処理方法及びステンレス鋼部品用の不動態化処理液 |
CN110129806A (zh) * | 2019-05-17 | 2019-08-16 | 浙江猫头鹰网络科技有限公司 | 抛光前处理酸洗液 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59190374A (ja) * | 1983-04-14 | 1984-10-29 | Ishikawajima Harima Heavy Ind Co Ltd | 酸化スケ−ルの溶解除去方法 |
DE9214890U1 (de) * | 1992-11-02 | 1993-01-07 | Poligrat Gmbh, 8000 Muenchen, De | |
JP2941948B2 (ja) * | 1994-09-26 | 1999-08-30 | カルゴン ベスタル, インコーポレイテッド | ステンレス鋼酸処理 |
RU2119553C1 (ru) * | 1997-04-18 | 1998-09-27 | Закрытое акционерное общество "Центр новых технологий "Оптрон" | Способ удаления оксидов и гидроксидов железа с поверхности изделий из стали |
CA2253679A1 (fr) | 1998-01-26 | 1999-07-26 | Elf Atochem S.A. | Passivation des aciers inoxydables en milieu acide organosulfonique |
AUPP762398A0 (en) * | 1998-12-09 | 1999-01-14 | Cairnscorp Technology Pty. Limited | Cleaning solutions containing citric acid and uses thereof |
WO2003101762A1 (en) * | 2002-05-28 | 2003-12-11 | Advanced Technology Materials, Inc. | Process for cleaning and repassivating semiconductor equipment parts |
US20060079424A1 (en) | 2004-09-23 | 2006-04-13 | Perry Stephen C | Buffered acid cleaner and method of production |
DE102007010538A1 (de) * | 2007-03-05 | 2008-09-11 | Poligrat Gmbh | Verfahren zum thermochemischen Passivieren von Edelstahl |
-
2008
- 2008-10-29 EP EP08018874A patent/EP2182095A1/de not_active Withdrawn
-
2009
- 2009-10-15 HU HUE09737363A patent/HUE026531T2/en unknown
- 2009-10-15 JP JP2011533578A patent/JP5586614B2/ja not_active Expired - Fee Related
- 2009-10-15 ES ES09737363.3T patent/ES2559387T3/es active Active
- 2009-10-15 US US13/126,827 patent/US9115433B2/en not_active Expired - Fee Related
- 2009-10-15 AU AU2009310094A patent/AU2009310094A1/en not_active Abandoned
- 2009-10-15 CA CA2741704A patent/CA2741704A1/en not_active Abandoned
- 2009-10-15 WO PCT/EP2009/007402 patent/WO2010049065A1/de active Application Filing
- 2009-10-15 EP EP09737363.3A patent/EP2352860B1/de not_active Not-in-force
Non-Patent Citations (1)
Title |
---|
See references of WO2010049065A1 * |
Also Published As
Publication number | Publication date |
---|---|
ES2559387T3 (es) | 2016-02-11 |
EP2182095A1 (de) | 2010-05-05 |
US20110309296A1 (en) | 2011-12-22 |
AU2009310094A1 (en) | 2010-05-06 |
WO2010049065A1 (de) | 2010-05-06 |
CA2741704A1 (en) | 2010-05-06 |
EP2352860B1 (de) | 2015-12-16 |
US9115433B2 (en) | 2015-08-25 |
JP2012506951A (ja) | 2012-03-22 |
HUE026531T2 (en) | 2016-06-28 |
JP5586614B2 (ja) | 2014-09-10 |
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