EP0058711B1 - Procede et produit pour passiver les surfaces en fer et en acier - Google Patents

Procede et produit pour passiver les surfaces en fer et en acier Download PDF

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Publication number
EP0058711B1
EP0058711B1 EP81902484A EP81902484A EP0058711B1 EP 0058711 B1 EP0058711 B1 EP 0058711B1 EP 81902484 A EP81902484 A EP 81902484A EP 81902484 A EP81902484 A EP 81902484A EP 0058711 B1 EP0058711 B1 EP 0058711B1
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EP
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Prior art keywords
acid
weight
treated
phosphonic
maleic acid
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EP81902484A
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German (de)
English (en)
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EP0058711A1 (fr
Inventor
Hermann Drosdziok
Jürgen Geke
Hans-Günther GERMSCHEID
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to AT81902484T priority Critical patent/ATE7932T1/de
Publication of EP0058711A1 publication Critical patent/EP0058711A1/fr
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Publication of EP0058711B1 publication Critical patent/EP0058711B1/fr
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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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors

Definitions

  • the invention relates to a method and means for passivating iron and steel surfaces chemically with the aid of aqueous solutions which react weakly alkaline and contain a combination of certain corrosion-inhibiting substances.
  • Passivation agents are also used as an additive to pressure baths, quenching water, such as for induction hardening, cooling circuits, such as in engine test benches, and also as hydraulic fluids.
  • passivation A number of methods are known for passivation. For example, it can be carried out with oils or fats or also corresponding plastic emulsions, although undesirable layers often form. It is therefore often advisable to passivate the metal surfaces with aqueous solutions that contain appropriate chemical additives.
  • Such corrosion inhibiting passivating agents for iron surfaces are, for example, alkali nitrites, alkali chromates, soaps, benzoates and alkanolamines. Alkanol amide salts of maleic acid have also been used for the passivation of iron and steel surfaces (see; e.g. EP-A-0002780).
  • Suitable maleic acid monoalkylamides are both amides with straight-chain and branched alkyl radicals having 6 to 14 carbon atoms, preferably having 8 to 10 carbon atoms.
  • Suitable alkanolamines are short-chain compounds such as mono-, di- and triisopropanolamine, n-propanolamine, N, N, N ', N'-tetrakis (2-hydroxyethyl) ethylenediamine and preferably mono-, di- and triethanolamine, in particular as Mixture, into consideration.
  • Suitable complexing phosphonic acids are: 1-hydroxyalkyl-1,1-diphosphonic acids, 1-aminoalkyl-1,1-diphosphonic acid, phosphonocarboxylic acids, such as in particular 2-phosphono-1,2,4-tricarboxylic acid and / or Phosphonic acids of the general formula in the means.
  • 1-Hydroxyethane-1,1-diphosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid and nitrilotrimethylenephosphonic acid have preferably proven successful.
  • the phosphonic acids can also be used as alkali salts or alkanolamine salts.
  • the free phosphonic acids can also be added to the corresponding solutions. In such a case, an excess of alkanolamine in the solution can then be used to adjust the pH to 7.5 to 10.5.
  • An essential feature of the combination according to the invention is the weight ratio of maleic acid monoalkylamide to alkanolamine, which should be 1 0.3 to 1:10 and preferably 1: to 1: 4.
  • the weight ratio of maleic acid monoalkylamide to phosphonic acid is the process according to the invention 1: 0.01 to 1: 0.5 and preferably 1: 0.1 to 1: 0.5.
  • a further increase in the addition of phosphonic acid is possible, but does not bring any additional synergistic effects.
  • the pH of the solution from 7.5 to 10.5 which is suitable for carrying out the process is not already achieved by the alkalinity of the substances used, it can be adjusted by adding a small amount of alkali.
  • the metal surfaces made of iron or steel can be treated at elevated temperatures between 30 and 100 ° C., but preferably at room temperature.
  • the agents can also contain further substances.
  • surfactants preferably nonionic low-foaming surfactants. Especially if cleaning is desired at the same time as the passivation or if greased or partially greased parts are to be treated in one operation.
  • low-foaming nonionic surfactants the addition products of ethylene or propylene oxide onto polypropylene glycol or polyethylene glycol and addition products of ethylene and / or propylene oxide onto mono- or polyalcohols, mono- or polyamines, fatty acids, amides and alkylphenols with an alkyl radical of preferably 8 to 20, in particular 12 to 18 carbon atoms.
  • the concentration in the aqueous passivation solution is between 0.005 to 0.3 percent by weight.
  • agents according to the invention may also be expedient in some cases to add builders, which increase the action of the surfactants, to the agents according to the invention in order to enhance the cleaning action.
  • builders which increase the action of the surfactants, to the agents according to the invention in order to enhance the cleaning action.
  • Ortho- or polymer phosphates and / or borates should be mentioned in particular.
  • a builder content in amounts of 0.2 to 2 percent by weight, based on the aqueous solution, is preferred.
  • the agents according to the invention can also contain alkanolamine soaps of short-chain fatty acids - d. H. of fatty acids with 6 to 12 carbon atoms -, for example caprylic or isononanoic acid, which reinforce the corrosion protection effect in a manner known per se and act as a solubilizer and as a foam regulator.
  • the solutions according to the invention may optionally also contain preservatives for preventing bacterial decomposition, such as chlorophenols, diphenyl derivatives, hexahydrotriazine derivatives and / or for non-ferrous metal inhibition, benztriazole, mercaptobenztriazole and lignin sulfonate in amounts of about 0.05 to 0.1 percent by weight.
  • preservatives for preventing bacterial decomposition such as chlorophenols, diphenyl derivatives, hexahydrotriazine derivatives and / or for non-ferrous metal inhibition, benztriazole, mercaptobenztriazole and lignin sulfonate in amounts of about 0.05 to 0.1 percent by weight.
  • agents used contain the components mentioned in the stated amounts. If desired, however, the corresponding agents can also be prepared in concentrated form in order to be diluted to the stated concentration immediately before use.
  • the corrosion protection obtained with the solutions according to the invention is considerably higher than the sum of the properties of the individual substances and exceeds the passivating agents used hitherto.
  • the outstanding corrosion protection properties of the method according to the invention were tested in the corrosion protection test according to DIN 51 360/2 with cast chips GG 30 at an exposure time of 2 hours.
  • the test solutions were prepared at room temperature with 20 ° hard water.
  • the pH of all test solutions was between 8.5 and 10.5; Test and comparison solution were adjusted to the same pH.
  • the concentration of the respective combination was 1, 1.5 and 2% in the DIN tests.
  • the comparative tests are listed under a) and the solutions according to the invention under b).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Detergent Compositions (AREA)
  • Chemical Treatment Of Metals (AREA)

Claims (18)

1. Procédé de passivage de surfaces en fer et en acier à l'aide de solutions aqueuses à réaction alcaline qui contiennent des inhibiteurs de corrosion, caractérisé en ce qu'on traite les surfaces métalliques avec des solutions à 0,5 à 5 % en poids qui contiennent une combinaison limpide soluble dans l'eau se composant de :
a) une ou plusieurs monoalcoylamides d'acide maléique,
b) une ou plusieurs alcanolamines,
c) un ou plusieurs acides phosphoniques possédant des propriétés complexantes,

le rapport pondéral de la monoalcoylamide d'acide maléique à l'alcanolamine étant de 1 : 0,3 à 1 : 10 et le rapport pondéral de la monoalcoylamide d'acide maléique à l'acide phosphonique étant de 1 : 0,01 à 1 : 0,5, la valeur du pH de la solution étant entre 7,5 et 10,5.
2. Procédé selon la revendication 1, caractérisé en ce que la surface métallique est traitée avec une solution qui contient de la mono-n ou -isoalcoylamide d'acide maléique ayant 6 à 14, de préférence 8 à 10 atomes de carbone dans le radical alcoyle.
3. Procédé selon les revendications 1 et 2, caractérisé en ce qu'on traite la surface métallique avec une solution qui contient de la mono-, di- et/ou triéthanolamine.
4. Procédé selon les revendications 1 à 3, caractérisé en ce qu'on traite la surface métallique avec une solution qui contient comme acide phosphonique de l'acide 1-hydroxyalcoyl-1,1-diphosphonique, de l'acide 1-aminoalcoyl-1,1-diphosphonique, de l'acide phosphonocarboxylique et/ou un acide phosphonique de formule
Figure imgb0014
dans laquelle
Figure imgb0015
5. Procédé selon les revendications 1 à 4, caractérisé en ce qu'on traite la surface métallique avec une solution qui contient comme acides phosphoniques de l'acide 1-hydroxyéthane-1,1-diphosphonique, de l'acide 2-phosphonobutane-1,2,4-tricarboxylique et/ou de l'acide nitrilotriméthylène-phosphonique.
6. Procédé selon les revendications 1 à 5, caractérisé en ce qu'on traite la surface métallique avec une solution dans laquelle le rapport pondéral de la monoalcoylamide d'acide maléique aux alcanolamines s'élève à 1 : 1 jusqu'à 1 : 4.
7. Procédé selon les revendications 1 à 6, caractérisé en ce qu'on traite la surface métallique avec une solution dans laquelle le rapport pondéral de la monoalcoylamide d'acide maléique à l'acide phosphonique s'élève à 1 : 0,1 jusqu'à 1 : 0,5.
8. Procédé selon les revendications 1 à 7, caractérisé en ce qu'on traite la surface métallique avec une solution qui contient supplémentairement des tensioactifs, de préférence des tensioactifs non ionogènes, en des quantités de 0,005 à 0,3 % en poids par rapport à la solution aqueuse.
9. Procédé selon les revendications 1 à 8, caractérisé en ce qu'on traite la surface métallique avec une solution qui contient supplémentairement des builders, de préférence des phosphates et/ou des borates, en des quantités de 0,2 à 2 % en poids par rapport à la solution aqueuse.
10. Agents de passivage de surfaces en fer et en acier, à base de solutions aqueuses à réaction alcaline contenant des inhibiteurs de corrosion, caractérisés en ce qu'ils contiennent une combinaison soluble dans l'eau avec limpidité se composant de :
a) une ou plusieurs monoalcoylamides d'acide maléique,
b) une ou plusieurs alcanolamines,
c) un ou plusieurs acides phosphoniques qui possèdent des propriétés complexantes

en des quantités en tout de 0,5 à 5 % en poids, le rapport pondéral de la monoalcoylamide d'acide maléique à l'alcanolamine étant de 1 : 0,3 à 1 : 10 et le rapport pondéral de la monoalcoylamide d'acide maléique à l'acide phosphonique étant de 1 : 0,01 à 1 : 0,5, la valeur du pH des solutions étant entre 7,5 et 10,5.
11. Agent selon la revendication 10, caractérisé en ce qu'il contient des mono-n- ou -iso-alcoylami- des d'acide maléique ayant 6 à 14, de préférence 8 à 10 atomes de carbone dans le radical alcoyle.
12. Agent selon les revendications 10 et 11, caractérisé en ce qu'il contient de la mono-, di- et/ou triéthanolamine.
13. Agent selon les revendications 10 à 12, caractérisé en ce qu'il contient comme acide phosphonique de l'acide 1-hydroxyalcoyl-1,1-diphosphonique, de l'acide 1-aminoalcoyl-1,1-diphosphoni- que, de l'acide phosphonocarboxylique et/ou un acide phosphonique de formule :
Figure imgb0016
dans laquelle
Figure imgb0017
14. Agent selon les revendications 10 à 13, caractérisé en ce qu'il contient comme acides phosphoniques de l'acide 1-hydroxyéthane-1,1-diphosphonique, de l'acide 2-phosphonobutane-1,2,4-tricarboxylique et/ou de l'acide nitrilotriméthylène-phosphonique.
. 15. Agent selon les revendications 10 à 14, caractérisé en ce que le rapport pondéral de la monoalcoylamide de l'acide maléique aux alcanolamines s'élève à 1 : 1 jusqu'à 1 : 4.
16. Agent selon les revendications 10 à 15, caractérisé en ce que le rapport pondéral de la monoalcoylamide d'acide maléique à l'acide phosphonique s'élève à 1 : 0,1 jusqu'à 1 : 0,5.
17. Agent selon les revendications 10 à 16, caractérisé en ce qu'il contient supplémentairement des tensioactifs, de préférence des tensioactifs non ionogènes, en des quantités de 0,005 à 0,3 % en poids par rapport à la solution aqueuse.
18. Agent selon les revendications 10 à 17, caractérisé en ce qu'il contient supplémentairement des builders, de préférence des phosphates et/ou borates, en des quantités de 0,2 à 2 % en poids par rapport à la solution aqueuse.
EP81902484A 1980-08-27 1981-08-19 Procede et produit pour passiver les surfaces en fer et en acier Expired EP0058711B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT81902484T ATE7932T1 (de) 1980-08-27 1981-08-19 Verfahren und mittel zum passivieren von eisenund stahloberflaechen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19803032226 DE3032226A1 (de) 1980-08-27 1980-08-27 Verfahren und mittel zum passivieren von eisen- und stahloberflaechen
DE3032226 1980-08-27

Publications (2)

Publication Number Publication Date
EP0058711A1 EP0058711A1 (fr) 1982-09-01
EP0058711B1 true EP0058711B1 (fr) 1984-06-13

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US (1) US4437898A (fr)
EP (1) EP0058711B1 (fr)
JP (1) JPH0132313B2 (fr)
BE (1) BE890068A (fr)
BR (1) BR8108760A (fr)
CA (1) CA1169337A (fr)
DE (2) DE3032226A1 (fr)
ES (1) ES8206660A1 (fr)
FR (1) FR2489372B1 (fr)
IT (1) IT1137644B (fr)
MX (1) MX157164A (fr)
WO (1) WO1982000665A1 (fr)
ZA (1) ZA815967B (fr)

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US4671934A (en) * 1986-04-18 1987-06-09 Buckman Laboratories, Inc. Aminophosphonic acid/phosphate mixtures for controlling corrosion of metal and inhibiting calcium phosphate precipitation
US5049311A (en) * 1987-02-20 1991-09-17 Witco Corporation Alkoxylated alkyl substituted phenol sulfonates compounds and compositions, the preparation thereof and their use in various applications
US4798675A (en) * 1987-10-19 1989-01-17 The Mogul Corporation Corrosion inhibiting compositions containing carboxylated phosphonic acids and sequestrants
EP0364030A1 (fr) * 1988-10-11 1990-04-18 Calgon Corporation Compositions synergiques et procédé pour l'inhibition de la corrosion de l'acier au carbone dans des systèmes aqueux
US4917737A (en) * 1989-03-13 1990-04-17 Betz Laboratories, Inc. Sealing composition and method for iron and zinc phosphating process
JPH04187782A (ja) * 1990-11-21 1992-07-06 Nippon Parkerizing Co Ltd ぶりきｄｉ缶用表面処理液
US5164234A (en) * 1991-01-24 1992-11-17 Henkel Corporation Treating an autodeposited coating with an alkaline solution containing organophosphonate ions
WO1997003226A1 (fr) * 1995-07-10 1997-01-30 Nippon Paint Co., Ltd. Traitements de surface de metaux, procede de traitement de surface de metaux et materiau metallique ayant subi un traitement de surface
DE19959588A1 (de) * 1999-12-10 2001-06-13 Henkel Kgaa Metallbehandlungsflüssigkeit für den neutralen pH-Bereich
EP1652969A1 (fr) * 2004-10-28 2006-05-03 Henkel Kommanditgesellschaft auf Aktien Composition et procédé de dérouillement
CN105986277A (zh) * 2015-02-03 2016-10-05 上海立昌环境工程有限公司 一种无磷中性除锈剂的制备及其应用
RU2593569C1 (ru) * 2015-06-03 2016-08-10 Публичное Акционерное Общество "Нижнекамскнефтехим" Ингибирующий состав для защиты металлов от кислотной коррозии
JP6566740B2 (ja) * 2015-06-24 2019-08-28 日本パーカライジング株式会社 水系金属表面処理剤、皮膜の製造方法及び皮膜付き金属材料
US10443135B1 (en) 2018-05-11 2019-10-15 Macdermid Enthone Inc. Near neutral pH pickle on multi-metals
CN109518173B (zh) * 2018-12-17 2021-04-23 熊映明 铝合金粉末喷涂预处理铬化线清洗水反向串联节水配置
CN109504959B (zh) * 2018-12-17 2021-04-23 熊映明 铝合金喷涂预处理无铬钝化线清洗水反向串联节水配置

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US2790779A (en) 1953-07-27 1957-04-30 Geigy Chem Corp Rust preventive compositions containing monoamidocarboxylic acids
DE1216066B (de) 1963-01-29 1966-05-05 Henkel & Cie Gmbh Verfahren zur Behandlung von entfetteten und mit einer sauren Loesung gebeizten Metallober-flaechen vor dem Emaillieren
US3770514A (en) * 1972-06-08 1973-11-06 American Cyanamid Co Chemical treatment of metal
DE2513735A1 (de) * 1974-04-01 1975-10-02 Calgon Corp Korrosionsschutzmittel
US4045253A (en) 1976-03-15 1977-08-30 Halliburton Company Passivating metal surfaces
DE2758123A1 (de) * 1977-12-24 1979-07-05 Basf Ag Korrosionsschutzmittel in waessrigen systemen
IT1098305B (it) * 1978-06-02 1985-09-07 Snam Progetti Antiruggine per sistemi acquosi e composizione lubrificante antiruggine
DE2962827D1 (en) 1978-10-13 1982-07-01 Ouest Union Chim Ind Corrosion inhibitor composition, process for its preparation and its use in protecting metal surfaces

Also Published As

Publication number Publication date
EP0058711A1 (fr) 1982-09-01
ES504978A0 (es) 1982-08-16
JPS57501289A (fr) 1982-07-22
FR2489372B1 (fr) 1986-04-11
MX157164A (es) 1988-10-31
BE890068A (fr) 1981-12-16
DE3164174D1 (en) 1984-07-19
IT8123630A0 (it) 1981-08-25
WO1982000665A1 (fr) 1982-03-04
US4437898A (en) 1984-03-20
IT1137644B (it) 1986-09-10
DE3032226A1 (de) 1982-04-01
ES8206660A1 (es) 1982-08-16
JPH0132313B2 (fr) 1989-06-30
BR8108760A (pt) 1982-07-06
CA1169337A (fr) 1984-06-19
FR2489372A1 (fr) 1982-03-05
ZA815967B (en) 1982-09-29

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