EP0683246B1 - Traitement de nettoyage et de passivation de métaux - Google Patents

Traitement de nettoyage et de passivation de métaux Download PDF

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Publication number
EP0683246B1
EP0683246B1 EP95301519A EP95301519A EP0683246B1 EP 0683246 B1 EP0683246 B1 EP 0683246B1 EP 95301519 A EP95301519 A EP 95301519A EP 95301519 A EP95301519 A EP 95301519A EP 0683246 B1 EP0683246 B1 EP 0683246B1
Authority
EP
European Patent Office
Prior art keywords
ion
treatment solution
cleaning
molybdate
amphoteric surfactant
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.)
Expired - Lifetime
Application number
EP95301519A
Other languages
German (de)
English (en)
Other versions
EP0683246A1 (fr
Inventor
Edward Albert Rodzewich
Barry Paul Gunagan
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.)
BetzDearborn Europe Inc
Original Assignee
BetzDearborn Europe Inc
Betz Europe Inc
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Filing date
Publication date
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Publication of EP0683246A1 publication Critical patent/EP0683246A1/fr
Application granted granted Critical
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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
    • 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
    • C23G1/24—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions

Definitions

  • the present invention relates to cleaning and passivating treatments for metals. More particularly, the present invention relates to cleaning and passivating treatments for metals which are essentially free of amines, alkanolamines, and phosphates.
  • the aqueous treatments of the present invention comprise amphoteric surfactants which were found to provide an excellent passivating film on ferrous surfaces.
  • the amphoteric surfactants of the present invention are caprylic acid derivatives of imidazoline compounds or sodium salts thereof.
  • In process cleaners are employed in the metal treatment industry to clean and passivate a metal surface. These types of aqueous cleaners are typically based on organic rust-proofing or passivating agents such as combinations of alkanolamines and fatty acids, surfactants, antifoam agents and/or phosphonates and possibly biocides and builders.
  • Cleaning and passivating agents which inhibit the corrosion of ferrous metal surfaces contain for example alkali nitrites, alkanolamines, soaps and benzoates.
  • Clean and passivate treatments are typically employed in applications which require good cleaning and temporary metal passivation. Treated parts may need to remain rust-free, while exposed in the manufacturing plant for from several hours up to 30 days. In order to maintain their rust prevention ability, these cleaners are not rinsed.
  • Current commercial cleaners typically employ alkanolamines such as monoethanolamine, diethanolamine or triethanolamine as a passivating agent for ferrous surfaces. The alkanolamine component inhibits flash rusting of ferrous iron parts during line stops or storage.
  • Typical cleaners also will include surfactants such as glycol ether compounds and phosphonate compounds which aid in cleaning of the parts.
  • U.S. Patent No. 4,578,208 which issued to Geke et al. discloses a cleaning and/or passivating composition and process which employs a phosphoric acid ester, an alkanolamine and a surfactant and optionally builders, nonferrous metal inhibitors and biocides.
  • U.K. Patent Specification 1,133,385 discloses a method of storage of corrodible metals wherein a layer of an aqueous solution of corrosion inhibitor is maintained in a wet condition on the surfaces to be protected. The wet condition of the treated surfaces is maintained by capillary action between surfaces in face-to-face contact.
  • Example 5 of this specification discloses a passivating solution which is free from amine, alkanolamine and phosphate, and which comprises sodium borate, sodium benzoate and polyoxyethylene-sorbitanmonooleate. The effective use of solutions containing a caprylic acid derivative of imidazoline is not disclosed.
  • amphoteric surfactants in accordance with the present invention obviates the need for amines, alkanolamines, phosphates and other currently environmentally undesirable materials in clean and passivate formulations.
  • the inventors found that compositions of a caprylic acid derivative of an imidazoline compound or a sodium salt thereof together with a borate ion and a molybdate ion as defined in claim 1 provide efficious passivation of ferrous metal surfaces.
  • the treatment solution of the present invention is substantially free of amines and alkanolamines, and phosphates. By substantially free, it is meant that these materials are not intentionally added as active components of the treatment solution.
  • the preferred treatment solution includes sodium molybdate. These compounds were found to allow reductions in the concentration of the amphoteric surfactant component without adversely affecting efficacy.
  • a defoamer such as a nonionic surfactant may be desirable in spray applications.
  • the molybdate ion is preferably added as sodium molybdate.
  • the formulation also includes a nonionic surfactant defoamer. The inventors found that such aqueous solutions provide effective rust protection.
  • the borate ion may be provided by a borate salt or by boric acid.
  • a cleaning and passivating treatment solution for ferrous metal surface comprising an aqueous solution of (a) from 0.05 to 5.0% by weight of a caprylic acid derivative of imidazoline amphoteric surfactant or sodium salt thereof, (b) a borate ion and (c) a molybdate ion wherein the weight ratio of caprylic acid derivative of imidazoline amphoteric surfactant or sodium salt thereof to borate ion (calculated as metaborate ion) is from 1:0.4 to 1:5 and the weight ratio of molybdate ion to caprylic acid derivative of imidazoline amphoteric surfactant or sodium salt thereof plus metaborate ion (BO 2 ) is more than 1:4, and said solution being essentially free of amine, alkanol amine and phosphate.
  • the formulation of the present invention includes amphoteric surfactants which are caprylic acid derivatives of an imidazoline compound or a sodium salt thereof.
  • the surfactants are present in the treatment solution at concentrations of from about 0.05% up to about 5% by weight.
  • amphoteric surfactants which are caprylic acid derivatives of an imidazoline (or sodium salts) include Monateric Cy-Na 50%, a sodium salt of 2-caprylic-1 (ethyl beta oxypropanoic acid) imidazoline; Monateric CYA-50, a capryl ampho-propionate; Monateric 1000, a capryl amphopropionate; and Miranol JAS concentrate which is a carboxylate derivative of capryl imidazoline.
  • Miranol is a trademark of Rhone-Poulenc and Monateric is a trademark of Mona Industries.
  • Amphopropionate is another name for imidazoline.
  • the preferred concentration of the surfactant is about 0.1 to 0.3% by weight.
  • the preferred concentration of sodium molybdate is from about 0.1 to 0.5% by weight.
  • the preferred concentration of sodium metaborate octahydrate is from about 0.1 to 0.5% by weight.
  • the clean and passivate formulation of the present invention is typically supplied in two concentrate packages which are diluted and mixed prior to application.
  • the first comprises the caprylic acid derivative of imidazoline compound or sodium salt thereof: sodium molybdate and sodium metaborate octahydrate in deionized water.
  • the second package comprises a nonionic surfactant defoaming agent.
  • Efficacy of the treatment solution of the present invention was evaluated in a chip test evaluation.
  • the test involved placing 4 g of cast iron chips on a filter paper in a plastic weighing dish, adding 50 ml of the test solution, allowing the solution to stand for 24 hours.
  • the filter paper is rinsed with tap water and examined for rust spots. Refer to ASTM D4627-92.
  • compositions and methods of the present invention are demonstrated by the following examples which are provided as illustrative and are not intended to limit the scope of the invention as set forth in the claims.
  • Table I shows that efficacious results are obtained at a relatively low treatment concentration with the combination of the present invention.
  • the treatment solution of the present invention is preferably supplied as a concentrate which is diluted with deionized water to form a working bath.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Cleaning Or Drying Semiconductors (AREA)
  • Detergent Compositions (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Claims (5)

  1. Solution de traitement de nettoyage et de passivation pour une surface de métal ferreux comprenant une solution aqueuse (a) de 0,05 à 5,0% en poids d'un dérivé acide caprylique d'imidazoline tensio-active amphotère ou d'un sel de sodium de celle-ci, (b) un ion de borate et (c) un ion de molybdate, dans laquelle le rapport de poids du dérivé acide caprylique d'imidazoline tensio-active amphotère ou de sel de sodium de celle-ci à ion de borate (calculé en tant qu'ion de métaborate) est de 1:0,4 à 1:5 et le rapport de poids d'ion de molybdate à dérivé acide caprylique d'imidazoline tensio-active amphotère ou sel de sodium de celle-ci plus ion de métaborate (BO2) est de plus de 1:4, et ladite solution étant essentiellement sans amine, alcanolamine et phosphate.
  2. Solution de traitement telle que revendiquée dans la revendication 1, dans laquelle ledit ion de borate est fourni par du sodium métaborate octahydrate.
  3. Solution de traitement telle que revendiquée dans la revendication 1 ou 2, dans laquelle ledit ion de molybdate est fourni par du sodium molybdate.
  4. Solution de traitement telle que revendiquée dans l'une quelconque des revendications précédentes, dans laquelle ladite solution de traitement comprend en outre un agent antimousse tensio-actif non ionique.
  5. Procédé de nettoyage et de passivation d'une surface de métal ferreux comprenant l'action de mettre en contact la surface de métal ferreux avec une solution de traitement aqueuse telle que revendiquée dans l'une quelconque des revendications précédentes.
EP95301519A 1994-05-20 1995-03-08 Traitement de nettoyage et de passivation de métaux Expired - Lifetime EP0683246B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US24655094A 1994-05-20 1994-05-20
US246550 1994-05-20

Publications (2)

Publication Number Publication Date
EP0683246A1 EP0683246A1 (fr) 1995-11-22
EP0683246B1 true EP0683246B1 (fr) 2000-07-19

Family

ID=22931164

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EP95301519A Expired - Lifetime EP0683246B1 (fr) 1994-05-20 1995-03-08 Traitement de nettoyage et de passivation de métaux

Country Status (6)

Country Link
EP (1) EP0683246B1 (fr)
AT (1) ATE194858T1 (fr)
CA (1) CA2143471A1 (fr)
DE (1) DE69518036T2 (fr)
ES (1) ES2148433T3 (fr)
PT (1) PT683246E (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102797004A (zh) * 2012-08-23 2012-11-28 李征 环保型有色金属表面处理剂及制备方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4759847A (en) * 1983-12-05 1988-07-26 Medbury Seward J Filter for the sorption of a petroleum product from a liquid

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1133385A (en) * 1966-03-18 1968-11-13 Fuji Iron & Steel Company Ltd Storage of corrodible metals
DE3316724A1 (de) * 1983-05-07 1984-11-08 Henkel KGaA, 4000 Düsseldorf Mittel und verfahren zur reinigung und passivierung von metallen im spritzverfahren
US4450088A (en) * 1983-05-19 1984-05-22 Basf Wyandotte Corporation Corrosion inhibited alcohol compositions
US4647392A (en) * 1985-12-27 1987-03-03 Texaco Inc. Monobasic-dibasic acid/salt antifreeze corrosion inhibitor
US4926449A (en) * 1988-02-22 1990-05-15 Burda Paul A Corrosion inhibition of closed cooling water auxiliary system for nuclear power plants
FR2686346B1 (fr) * 1992-01-21 1994-09-30 Bp Chemicals Snc Composition antigel et fluide aqueux.

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4759847A (en) * 1983-12-05 1988-07-26 Medbury Seward J Filter for the sorption of a petroleum product from a liquid

Also Published As

Publication number Publication date
EP0683246A1 (fr) 1995-11-22
DE69518036D1 (de) 2000-08-24
ES2148433T3 (es) 2000-10-16
DE69518036T2 (de) 2001-03-22
CA2143471A1 (fr) 1995-11-21
PT683246E (pt) 2000-11-30
ATE194858T1 (de) 2000-08-15

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