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WO1994024333A1 - Procede destine a accroitre la resistance a la corrosion d'un acier inoxydable - Google Patents

Procede destine a accroitre la resistance a la corrosion d'un acier inoxydable Download PDF

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Publication number
WO1994024333A1
WO1994024333A1 PCT/EP1994/001090 EP9401090W WO9424333A1 WO 1994024333 A1 WO1994024333 A1 WO 1994024333A1 EP 9401090 W EP9401090 W EP 9401090W WO 9424333 A1 WO9424333 A1 WO 9424333A1
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WO
WIPO (PCT)
Prior art keywords
mol
acids
acid
indicates
oxidizing
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.)
Ceased
Application number
PCT/EP1994/001090
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German (de)
English (en)
Inventor
Wolfgang Preibsch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ecolab GmbH and Co OHG
Original Assignee
Henkel Ecolab GmbH and Co KG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel Ecolab GmbH and Co KG filed Critical Henkel Ecolab GmbH and Co KG
Publication of WO1994024333A1 publication Critical patent/WO1994024333A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • C23C22/60—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 alkaline aqueous solutions with pH greater than 8
    • C23C22/62—Treatment of iron or alloys based thereon

Definitions

  • the invention relates to a chemical process for increasing the corrosion resistance of stainless steel.
  • steels are referred to as non-rusting or rust-free, in which rust formation is prevented under usual environmental conditions such as atmospheric oxygen, moisture and in aqueous solutions.
  • corrosion-resistant or acid-resistant steels resist harsh corrosion conditions such as acids and salt solutions.
  • these steels are called stainless steels.
  • Annealing colors are also produced on stainless steels by annealing in air, the color scale of which depends on the respective annealing temperature and their intensity as well as on the annealing duration. They occur at temperatures from around 250 ° C. The coloring begins with a yellow tone. When the temperature increases, a yellow-brown color occurs. Further temperature increases cause blue, red and violet tints. However, the oxidation of the surface carried out in this form greatly reduces the corrosion resistance of the steel. Products colored in this way can therefore not be used either in the outside atmosphere or when exposed to aggressive media ("stainless steels", loc. Cit. P. 226).
  • the object of the invention is to achieve the corrosion resistance of high-alloy steels by means of a chrome-free chemical surface treatment of low-alloy stainless steels.
  • the invention accordingly relates to a chromium-free process for producing a colored corrosion-protective layer on stainless steel, which has a molybdenum content of less than 1% by weight, characterized in that the steel surfaces are treated with an aqueous alkaline solution at temperatures between 50 ° C and 240 ° C treated, which contains at least one complexing agent and at least one oxidizing agent in deionized water and has a pH between 12 and 14.
  • the object is therefore achieved by treating the surface of low-alloy steels with a solution containing complexing agents and oxidizing agents in demineralized water with a pH of at least 12 at temperatures between 50 ° C. and 240 ° C.
  • the treatment time at a given treatment temperature depends on the complexing agent used and on the desired layer thickness of the corrosion-protective surface layer to be built up and is between about one and about 48 hours. Depending on the thickness of the corrosion-protective layer, the surface takes on a color from golden yellow to slightly brownish, violet, deep brown to black. Because of the lower apparatus requirements, an unpressurized process control at temperatures between 50 and 100 ° C. is preferred. When the process is carried out in a pressure reactor at temperatures between 100 and 240 ° C. under the water however, treatment times can be shortened due to pressure.
  • the method is applicable to ferritic, martensitic and austenitic steels.
  • the alkaline pH of the treatment solution can be adjusted with alkali metal hydroxide, with ammonia or with organic amines.
  • alkali metal hydroxides and in particular sodium hydroxide are preferred.
  • a large number of complexing agents suitable according to the invention are known. They can belong to different chemical groups. The following are suitable individually or in a mixture:
  • hydroxypolycarboxylic acids such as tartaric acid and citric acid
  • nitrogen-containing mono- or polycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylethylenediaminetriacetic acid, diethy- lentria inpentaacetic acid, hydroxyethyliminodiacetic acid, nitrilodiacetic acid, 3-n-propanoic acid, n-propanoic acid, (ß-hydroxyethyl) glycine, N- (1,2-dicarboxy-2-hydroxyethyl) glycine, N- (1,2-dicarboxy-2-hydroxyethyl) aspartic acid or nitrilotriacetic acid (NTA), c ) geminal diphosphonic acids such as l-hydroxyethane-ll-diphosphonic acid (HEDP), their higher homologues with up to 8 carbon atoms and derivatives thereof containing hydroxyl or amino groups
  • EDTA Complexing agents from the group of nitrogen-containing polycarboxylic acids, in particular EDTA, are preferred.
  • these Komolex formers are at least partially present as anions. It is immaterial whether they are introduced in the form of acids or in the form of water-soluble salts. In the case of use as salts, alkali, ammonium or alkylammonium salts, in particular sodium salts, are preferred.
  • Suitable oxidizing agents are peroxides such as hydrogen peroxide and alkali or alkaline earth peroxides, salts forming hydrogen peroxide and compounds such as percarbonates, in particular sodium percarbonate, perborates and salts of peroxo acids such as peroxomonosulfuric acid (Caro's acid) or peroxodisulfuric acid. Salts of oxidizing acids without a peroxo group, such as chlorates or bromates, are also suitable.
  • the oxidizing agents can be used individually or in a mixture with one another.
  • the effective concentrations of the complexing agents in the treatment baths are in the range of 0.01 to 0.075 mol / 1. They depend on the "denticity" of the chelating molecules. For hexadentate complexing agent molecules such as EDTA, the effective concentrations are in the range from 0.01 to 0.05 mol / 1, preferably 0.02 to 0.04 mol / 1. Correspondingly higher concentrations should be selected for complexing agent molecules with lower denticity. For example, for the preferably tidentate coordinating nitrilotriacetic acid, the effective concentrations are in the range 0.015 to 0.075 mol / 1, preferably 0.03 to 0.06 mol / 1. Tetrasodium EDTA as a preferred complexing agent is therefore particularly effective in concentrations between 0.7 and 1.3% by weight.
  • the concentrations of the H2O2-releasing oxidizing agents are selected such that the calculated total concentration of H2O2 is between 0.05 and 0.5 mol / 1, preferably between 0.08 and 0.15 mol / 1.
  • Sodium perborate is preferably used, for example as sodium perborate monohydrate ("NaB ⁇ 3.H2 ⁇ "). Concentrations of about 1 to 5% by weight are particularly effective. Salts of oxidizing acids without a peroxo group, in particular chlorates or bromates, are used in concentrations between 0.05 and 0.5 mol / l, preferably 0.08-0.15 mol / 1. Higher concentrations are possible, but have no further advantage.
  • the amount of alkali required to adjust the pH depends on whether the complexing agents and / or the oxidizing agents are introduced as salts or as free acids. It is to be chosen so that the pH range according to the invention is adjusted from 12 to 14, preferably 12.5 to 13.5. For example, if you use a solution in deionized water that contains 1% by weight of tetrasodium EDTA and 1% by weight of sodium perborate monohydrate. holds, the required amount of NaOH is at least 2% by weight. Higher pH values accelerate the layer formation.
  • Test sheets made of V2A steel (material no. 1.4301) were immersed at a temperature of 80 ° C for one, ten and 24 hours in sample and comparison solutions of the composition given in Table 1.
  • complexing agents and oxidizing agents were dissolved in demineralized water and the specified pH was adjusted by adding 50% by weight sodium hydroxide solution.
  • the sheets were rinsed with deionized water and dried with compressed air. The color of the sheets, which indicates the formation of the corrosion protection coating, was assessed optically. The results are shown in Table 1.
  • Test sheets made of V2A steel (material no. 1.4301) were placed in a nickel autoclave together with 1 1 solution of the composition according to Example 2. The autoclave was heated to 190 ° C within one hour (autogenous pressure 14-15 bar), held at this temperature for different times and then cooled to approx. 90 ° C within 45 minutes. The sheets were removed, cooled and rinsed by immersion in demineralized water, dried with compressed air and the color was assessed. Result :

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

Procédé, sans intervention de chrome, pour l'obtention d'une couche anticorrosion colorée sur un acier inoxydable présentant une teneur en molybdène inférieure à 1 % en poids, caractérisé en ce qu'on traite la surface de l'acier par une solution alcaline aqueuse, à des températures comprises entre 50 °C et 240 °C, ladite solution renfermant au moins un agent complexant et au moins un agent oxydant dans une eau complètement déminéralisée, et présentant un pH compris entre 12 et 14.
PCT/EP1994/001090 1993-04-16 1994-04-08 Procede destine a accroitre la resistance a la corrosion d'un acier inoxydable Ceased WO1994024333A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19934312417 DE4312417A1 (de) 1993-04-16 1993-04-16 Verfahren zur Erhöhung der Korrosionsbeständigkeit von nichtrostendem Stahl
DEP4312417.8 1993-04-16

Publications (1)

Publication Number Publication Date
WO1994024333A1 true WO1994024333A1 (fr) 1994-10-27

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ID=6485598

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1994/001090 Ceased WO1994024333A1 (fr) 1993-04-16 1994-04-08 Procede destine a accroitre la resistance a la corrosion d'un acier inoxydable

Country Status (2)

Country Link
DE (1) DE4312417A1 (fr)
WO (1) WO1994024333A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6277327B1 (en) 1998-01-29 2001-08-21 Tohoku Electric Power Company, Inc. Method for the anticorrosive treatment of waste plastics treating equipment

Families Citing this family (26)

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AU3596295A (en) * 1994-09-26 1996-04-19 E.R. Squibb & Sons, Inc. Stainless steel alkali treatment
US6521052B2 (en) * 2000-02-10 2003-02-18 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Surface treatment
US6341612B1 (en) 2000-03-09 2002-01-29 Steris Inc Two compartment container for neutralizing used cleaning solutions
US6550487B1 (en) 2000-03-09 2003-04-22 Steris Inc. Apparatus for removing deposits from enclosed chambers
US6770150B1 (en) 2000-03-09 2004-08-03 Steris Inc. Process for removing deposits from enclosed chambers
CA2413888A1 (fr) * 2000-06-22 2001-12-27 United States Filter Corporation Protection contre la corrosion utilisant un donneur de peroxyde d'hydrogene
US6716359B1 (en) 2000-08-29 2004-04-06 United States Filter Corporation Enhanced time-based proportional control
US6620315B2 (en) 2001-02-09 2003-09-16 United States Filter Corporation System for optimized control of multiple oxidizer feedstreams
US6776926B2 (en) 2001-08-09 2004-08-17 United States Filter Corporation Calcium hypochlorite of reduced reactivity
US6991735B2 (en) 2002-02-26 2006-01-31 Usfilter Corporation Free radical generator and method
US7108781B2 (en) 2002-02-26 2006-09-19 Usfilter Corporation Enhanced air and water purification using continuous breakpoint halogenation with free oxygen radicals
US12103874B2 (en) 2006-06-06 2024-10-01 Evoqua Water Technologies Llc Ultraviolet light activated oxidation process for the reduction of organic carbon in semiconductor process water
US10343939B2 (en) 2006-06-06 2019-07-09 Evoqua Water Technologies Llc Ultraviolet light activated oxidation process for the reduction of organic carbon in semiconductor process water
WO2007146671A2 (fr) 2006-06-06 2007-12-21 Fluid Lines Procédé d'oxydation activé par la lumière ultaviolette destiné à la réduction de carbone organique dans l'eau de traitement de semiconducteurs
US8741155B2 (en) 2007-04-03 2014-06-03 Evoqua Water Technologies Llc Method and system for providing ultrapure water
US8753522B2 (en) 2007-04-03 2014-06-17 Evoqua Water Technologies Llc System for controlling introduction of a reducing agent to a liquid stream
US9365435B2 (en) 2007-04-03 2016-06-14 Evoqua Water Technologies Llc Actinic radiation reactor
US9725343B2 (en) 2007-04-03 2017-08-08 Evoqua Water Technologies Llc System and method for measuring and treating a liquid stream
US8961798B2 (en) 2007-04-03 2015-02-24 Evoqua Water Technologies Llc Method for measuring a concentration of a compound in a liquid stream
US9365436B2 (en) 2007-04-03 2016-06-14 Evoqua Water Technologies Llc Method of irradiating a liquid
DE102008012762B4 (de) * 2008-03-05 2023-02-09 DEWE Brünofix GmbH Gleitlager
US8591730B2 (en) 2009-07-30 2013-11-26 Siemens Pte. Ltd. Baffle plates for an ultraviolet reactor
EP2527301B1 (fr) 2011-05-26 2016-04-27 Evoqua Water Technologies GmbH Procédé et dispositif pour le traîtement de l'eau
DE102012108513B4 (de) 2012-09-12 2014-12-24 Benteler Automobiltechnik Gmbh Verfahren zur Herstellung eines Kraftfahrzeugwärmetauschers mit Oxidschicht
US11161762B2 (en) 2015-01-21 2021-11-02 Evoqua Water Technologies Llc Advanced oxidation process for ex-situ groundwater remediation
CA2918564C (fr) 2015-01-21 2023-09-19 Evoqua Water Technologies Llc Procede d'oxydation avance pour retablissement d'eaux souterraines hors site

Citations (6)

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Publication number Priority date Publication date Assignee Title
DE1521732A1 (de) * 1965-10-24 1969-09-18 Dow Chemical Co Passivierung einer Eisenmetalloberflaeche
CH481225A (de) * 1966-01-15 1969-11-15 Borg Holding Ag Verfahren zum Behandeln von Eisen enthaltenden Metalloberflächen sowie Anwendung des Verfahrens
DE2210720A1 (de) * 1972-03-06 1973-09-20 Oxford Chemicals Inc Schwaerzungsmittel
US4045253A (en) * 1976-03-15 1977-08-30 Halliburton Company Passivating metal surfaces
EP0086245A1 (fr) * 1980-12-05 1983-08-24 Dowell Schlumberger Corporation Composition aqueuse acide pour le nettoyage de métaux et son procédé d'application
US5015298A (en) * 1989-08-22 1991-05-14 Halliburton Company Composition and method for removing iron containing deposits from equipment constructed of dissimilar metals

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1521732A1 (de) * 1965-10-24 1969-09-18 Dow Chemical Co Passivierung einer Eisenmetalloberflaeche
CH481225A (de) * 1966-01-15 1969-11-15 Borg Holding Ag Verfahren zum Behandeln von Eisen enthaltenden Metalloberflächen sowie Anwendung des Verfahrens
DE2210720A1 (de) * 1972-03-06 1973-09-20 Oxford Chemicals Inc Schwaerzungsmittel
US4045253A (en) * 1976-03-15 1977-08-30 Halliburton Company Passivating metal surfaces
EP0086245A1 (fr) * 1980-12-05 1983-08-24 Dowell Schlumberger Corporation Composition aqueuse acide pour le nettoyage de métaux et son procédé d'application
US5015298A (en) * 1989-08-22 1991-05-14 Halliburton Company Composition and method for removing iron containing deposits from equipment constructed of dissimilar metals

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6277327B1 (en) 1998-01-29 2001-08-21 Tohoku Electric Power Company, Inc. Method for the anticorrosive treatment of waste plastics treating equipment

Also Published As

Publication number Publication date
DE4312417A1 (de) 1994-10-20

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