US3682713A - Process for applying protective coatings on aluminum,zinc and iron - Google Patents

Process for applying protective coatings on aluminum,zinc and iron Download PDF

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Publication number
US3682713A
US3682713A US49925A US3682713DA US3682713A US 3682713 A US3682713 A US 3682713A US 49925 A US49925 A US 49925A US 3682713D A US3682713D A US 3682713DA US 3682713 A US3682713 A US 3682713A
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zinc
iron
acid
aluminum
per liter
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US49925A
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Christian Ries
Gunter Stolzenfels
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Gerhard Collardin GmbH
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Gerhard Collardin GmbH
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    • 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
    • C23C22/68—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 solutions with pH between 6 and 8
    • 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
    • C23C22/34—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 containing fluorides or complex fluorides
    • 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
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment

Definitions

  • a process for applying a protective coating on aluminum, zinc and iron under substantially identical operating conditions which consists essentially of applying to the metal surfaces of aluminum, zinc and iron of a complex fluoride coating solution free from chromic acid, phosphoric acid and oxalic acid having a concentration of from 0.1 to 15 gm. per liter, based on the metal content, of complex fluorides of metals selected from the group consisting of boron, titanium, zirconium and iron, from 0.1 to gm. per liter of free fluoride ions and from 0.5 to 30 gm.
  • the applied coatings can be post-passivated with solutions containing chromic or phosphoric acids.
  • Chromate coatings are generally applied to aluminum. These process conditions are, however, not suitable for applying of protective coatings onto iron and steel.
  • the problem of treating steel and galvanized, especially Sendzimir-galvanized, surfaces and also aluminum surfaces with the same process often occurs in practice, particularly in strip operations. It is relatively expensive to introduce a special solution for each of the mentioned metals.
  • An object of the invention is the development of a process of coating diverse metals such as aluminum, iron and zinc under identical operating conditions using a complex fluoride coating solution.
  • a further object of the invention is the development 'ice of a process for applying a protective coating on aluminum, zinc and iron under substantially identical operating conditions which consists essentially of applying to the metal surfaces of aluminum, zinc and iron of a. complex fluoride coating solution free from chromic acid, phosphoric acid and oxalic acid having a concentration of from 0.1 to 15 gmper liter, based on the metal content, of complex fluorides of metals selected from the group consisting of boron, titanium, zirconium and iron, from 0.1 to 10 gm. per liter of free fluoride ions and from 0.5 to 30 gm. per liter, calculated as sodium m-nitrobenzene sulfonate, of an oxidizing agent, at a pH of from 3.0 to 6.8 for a time sufficient to form a coating.
  • the invention solves the problem of the development of a simple process for manufacturing of protective coatings on aluminum, iron or steel and zinc or zinc galvanized surfaces, which treats the different metal surfaces under identical operating conditions.
  • the new process is characterized in that the metal surfaces are treated until a coating has been formed with a solution, free of chromic acid, phosphoric acid and oxalic acid, which contains complex fluorides of boron, titanium, zirconium or iron in amounts of from 0.1 to 15 gm. per liter, calculated as the metal ion content, containing from 0.1 to 10 gm. per liter of free fluoride ions and 0.5 to 30 gm. per liter of oxidizing agents, calculated as sodium m-nitrobenzene sulfonate.
  • the formed protective coating can eventually be after-treated with chromic acid and/or phosphoric acid containing solutions.
  • the mentioned complex fluorides being utilized are water-soluble compounds which can be added directly into solution or which can be formed in the solution by addition of their components.
  • the latter process can be carried out through addition of water-soluble salts of the metals as well as the corresponding amounts of fluoride ions.
  • titanyl sulfate or zinconyl chloride can be utilized.
  • the iron ions can be added, in addition to the complex fluoride as a water-soluble salt such as the sulfate, nitrate or chloride.
  • the treatment solutions of this invention can also contain several of the metal ions or mixtures of different salts of the metals.
  • fluoride ions are not added to the treatment solutions in the form of complex fluorides, then they are added as hydrofluoric acid or its neutral or acid salts.
  • An excess of fluoride ions above the stoichiometrically required quantity for the forming of the complex fluorides is useful if the desired pH range is maintained.
  • the solutions of this invention contain an oxidizing agent, preferably sodium m-nitrobenzene sulfonate.
  • an oxidizing agent preferably sodium m-nitrobenzene sulfonate.
  • the free acid can also be utilized.
  • this oxidizing agent it is possible to vary the treatment time of the metal surface to a very large extent.
  • the m-nitrobenzene sulfonates other oxidation agents can be used.
  • oxidation agents under consideration are those known as oxidizing acceleration agents for phosphatizing solutions, such as for example, alkali metal nitrates, nitrites, chlorates, bromates; hydrogen peroxide and its addition products; aliphatic and aromatic nitro and nitroso compounds, such as nitroguanidine, picric acid, nitrophenols; as well as dinitrotoluene sulfonic acid and its alkali metal salts and quinone. Mixtures of different oxidizing agents can also be used.
  • the oxidizing agents are preferably utilized in amounts of from 0.5 to 30 gm. per liter, preferably from 2 to 15 gm. per liter, calculated as sodium m-nitrobenzene sulfonate. In other words, if another oxidizing agent is utilized, it is used in amounts which would give an active oxygen release equivalent to the range of sodium m-nitrobenzene sulfonate.
  • metal salts which form an insoluble oxide in the coating and which are between magnesium and hydrogen inthe electromotive series. These are preferably water-soluble salts of zinc, nickel, cobalt and trivalent chromium. The amounts of these metal salts which are utilized amount to about 0.1 to 5 gm. per liter, preferably 0.2' to 2 gm. per liter, based on the metal salt added.
  • the treatment solutions must be practically free of chromic acid or chromium-(VI)-compounds, oxalic acids or oxalates and phosphoric acid or phosphates. These compounds or their corresponding anions interfere with the forming of the coating according to this invention, since they themselves are film-forming anions. Even relatively small quantities, for instance, of phosphates, ,decrease already the adhesion of varnish layers. Chromic acid and chromium-(VI)-compounds must moreover be excluded because of their poisonousness and .the herewith connected expensive waste water purification.
  • the pH value of the acid solutions lies preferably in the range above 3.0 to 6.8. Optimum operating pH ranges and optimum spray times will vary depending upon the metal substrate and the selection of coating solutions in accordance with the invention. A pH range of 3.6 to 4.9 has been proven to be particularly suitable. The adjustment of the pH value can be carried out with alkalis or acids.
  • the treatment time is preferably short and amounts in general to 3 to 180 seconds, particularly 5 to 60 seconds.
  • the treatment time is consequently so short, in strip installations with very high strip speeds, one can operate without the need for applying specially large baths or spraying zones.
  • the operating temperature of the acid solutions lies between and 95 C., preferably between 40 and 65 C.
  • the solutions can be applied with a dipping or brushing process; preferably, however, they are applied in a spraying process or by means of roll-coaters.
  • the metal surfaces are cleansed or degreased before the treatment, according to this invention. This cleansing and degreasing can be carried out by means of solvents or with the customary alkaline, neutral or acid cleansers and depends upon the degree of soil.
  • This post-passivating can be carried out with a diluted solution of chromic acid and/or phosphoric acid or acid chromates and/or phosphates.
  • concentration of the chromic acid and/or the phosphoric acid or their salts lies generally betwees 0.01 and 5 gm. per liter.
  • a preferred execution form of the invention consists of the after-treatment of the protective coatings'by'means of diluted chromic acid which contains chromium- (III)-ions.
  • concentrations applied lie generally between 0.2 and 3 gm. per liter CrO and 0.05 to 1 gm. per liter Cr O-
  • the concentrations applied lie generally between 0.2 and 3 gm. per liter CrO and 0.05 to 1 gm. per liter Cr O-
  • the concentrations applied lie generally between 0.2 and 3 gm. per liter CrO and 0.05 to 1 gm. per liter Cr O-
  • the concentrations applied lie generally between 0.2 and 3 gm. per liter CrO and 0.05 to 1 gm. per liter Cr O-
  • the concentrations applied lie generally between 0.2 and 3 gm. per liter CrO and 0.05 to 1 gm. per liter Cr O-
  • the concentrations applied lie generally between 0.2 and 3 gm. per liter CrO and 0.05 to
  • the treatment baths of the invention can be prepared through dissolving the above-stated compounds or through diluting of corresponding concentrates. They can be used during long periods of time and can again and again be replenished to constant points with the starting materials.
  • the points of a solution are hereby defined in the customary way as the amount in ml. of 0.1 N NaOH which is necessary to titrate 10 ml. of bath solution to the turning point of bromophenol blue (free acid) or phenolphthalein '(total acid).
  • An additional pH correction may be necessary after replenishing several times if the baths are replenished with'the same liquid or solid concentrates.
  • baths are preferably replenished with solutions or concentrates, which contain complex fluorides of boron, titanium,.zirc onium and/or iron and 1 at least one oxidizing agent and which have an acid ratio of freeacid to .total acid of 1:1.05 to 1:3'.0, preferably 1:1.5 m 2.5.
  • The'process of the invention produces on aluminum, iron or steel, zinc and zinc galvanized surfaces, evenly thin, easily deformable, homogeneous coatings which give a good corrosion protection and possess an excellent varnish adhesion.
  • the coatings on steel are mouse-grey to bluish iridescent, those on zinc and aluminum, dulllight grey to light yellowish iridescent.
  • the process can easily be maintained, and the baths possess a very long life. The same baths can be used under equal operating conditions for all of the mentioned metal surfaces.
  • the pH value was adjusted to 6.6.
  • the treatment temperature amounted to 35 C. and the treatment time to l 120 seconds.
  • the treated strips were rinsed subsequently be changed.
  • the layer-forming treatment solution was, however, the same for all strip types. Thin, evenly good, deformable coatings with excellent adhesion for paint and plastic were obtained with this treatment solution on aluminum and on Sendzimir-galvanized material as well as on steel.
  • Example 2 In changing from zinc to steel surfaces or to aluminum surfaces neither the bath composition nor the operating conditions, such as for instance, the transporting speed (treatment time), pH valueand bath temperature, had to Example 2 Equally good results were obtained following the process of Example 1 in using a solution of the following composition instead of the treatment solution mentioned in Example. 1:
  • Example 3 In a spray installation coatings were applied successively to sample strips of steel, galvanized steel and aluminum respectively. In each case the metal strips were degreased and cleaned with a conventional alkaline cleaner, rinsed with cold water and then sprayed With :a solution of the following composition:
  • the treatment temperature was maintained at approximately 65 C. and after treatment the metal strips were rinsed with cold water and post-passivated with chromic acid solution (0.06 percent by wt. chromium-IV-ions and 0.02 percent by wt. chrornium-III-ions) and thereafter dried.
  • the time of spray treatment was varied, with corresponding variations in coating weight.
  • a 60-second spray on steel gave a coating of 0.83 -gm./meter
  • a 60-second spray on galvanized steel gave a coating weight of 2.1 gm./meter and a 60-second spray on aluminum gave a coating weight of 2.4 gm/meter? In all cases the coating was of a light gray amorphous appearance, uniform and evenly distributed with excellent adhesion for paint and excellent corrosion resistance properties.
  • the coating solution was replenished with zinc fiuoborate so as to maintain the zinc concentration above 4.0 gm./liter and preferably above 10 gm./liter.
  • the coating solution may be replenished by adding zinc oxide and fluoboric acid thereto to produce zinc fiuoborate in situ.
  • the fluoride activity of the bath should be maintained at a concentration equivalent to 2.0 gum/liter of fluoride ion or greater by the addition of ammonium fluoride as necessary.
  • the nitrite concentration is preferably maintained at 0.25 gm./ liter calculated as nitrite, or greater.
  • the pH is preferably maintained between about 4.3 and 4.9 by the addition of sodium hydroxide.
  • the addition of zinc fiuoborate can be conveniently controlled by conventional zinc titration techniques customarily employed in producing zinc phosphate coatings on metal.
  • the fluoride ion content can be conveniently controlled by use of electronic equipment, such as the commercially available Lineguard Meter No. 101A (described in United States Patent 3,350,284).
  • Nitrite concentration is conveniently controlled by conventional titration methods, such as a potassium permanganate titration conventionally employed in metal coating processes utilizing nitrite as an oxidizing agent.
  • a process for applying a protective coating on aluminum, zinc and iron under substantially identical operating conditions which consists essentially of successively applying to the metal surfaces of aluminum, zinc and iron of a complex fluoride coating solution free from chromic acid, phosphoric acid and oxalic acid having a concentration of from 0.1 to 15 gm. per liter, based on the metal content, of complex fluorides of metals selected from the group consisting of boron, titanium, zirconium and iron, from 0.1 to 10 gm. per liter of free fluoride ions and from 0.5 to 30 gm. per liter, calculated as sodium m-nitrobenzene sulfonate, of an oxidizing agent, at a pH of from above 3.0 to 6.8 for a time suflicient to form a coating.

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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)
  • Catalysts (AREA)
US49925A 1969-06-28 1970-06-25 Process for applying protective coatings on aluminum,zinc and iron Expired - Lifetime US3682713A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE1933013A DE1933013C3 (de) 1969-06-28 1969-06-28 Verfahren zur Erzeugung von Schutzschichten auf Aluminium, Eisen und Zink mittels komplexe Fluoride enthaltender Lösungen

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JP (1) JPS4824618B1 (enrdf_load_stackoverflow)
BE (1) BE752626A (enrdf_load_stackoverflow)
DE (1) DE1933013C3 (enrdf_load_stackoverflow)
FR (1) FR2051358A5 (enrdf_load_stackoverflow)
GB (1) GB1316865A (enrdf_load_stackoverflow)
NL (1) NL7009376A (enrdf_load_stackoverflow)
SE (1) SE358422B (enrdf_load_stackoverflow)
ZA (1) ZA704412B (enrdf_load_stackoverflow)

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DE2433704A1 (de) * 1973-07-13 1975-01-30 Amchem Prod Metallbehandlungsmittel, verfahren zu ihrer herstellung und ihre anwendung
JPS5098450A (enrdf_load_stackoverflow) * 1974-01-02 1975-08-05
DE2500075A1 (de) * 1974-01-02 1975-08-14 Amchem Prod Mittel und verfahren zum ueberziehen von aluminium
US3920486A (en) * 1973-05-10 1975-11-18 Oxy Metal Industries Corp Method of blackening ferrous metal surfaces
US4086092A (en) * 1977-04-18 1978-04-25 Polychrome Corporation Process for making photosensitive lithographic printing plates involving sequentially coating with potassium zirconium fluoride and sodium silicate
US4110129A (en) * 1977-02-03 1978-08-29 Oxy Metal Industries Corporation Post treatment of conversion-coated zinc surfaces
JPS53125238A (en) * 1977-04-09 1978-11-01 Nippon Paint Co Ltd Regenerating method for surface treating liquid for aluminum and its alloy
US4148670A (en) * 1976-04-05 1979-04-10 Amchem Products, Inc. Coating solution for metal surface
US4191596A (en) * 1978-09-06 1980-03-04 Union Carbide Corporation Method and compositions for coating aluminum
DE3031270A1 (de) * 1979-09-06 1981-03-19 Richardson Chemical Co., Des Plaines, Ill. Verfahren zur chromfreien oder chromarmen passivierung von metalloberflaechen und bad zur durchfuehrung des verfahrens
US4273592A (en) * 1979-12-26 1981-06-16 Amchem Products, Inc. Coating solution for metal surfaces
US4294627A (en) * 1979-06-07 1981-10-13 Metal Box Limited Treatment of tinplate surfaces
US4338140A (en) * 1978-02-21 1982-07-06 Hooker Chemicals & Plastics Corp. Coating composition and method
DE3213384A1 (de) * 1981-04-16 1982-12-09 Hooker Chemicals & Plastics Corp., 48089 Warren, Mich. Waessrige saure loesung und verfahren fuer die behandlung aufnahmefaehiger metallsubstrate zur verleihung eines passivierungsfilms
US4391652A (en) * 1982-01-29 1983-07-05 Chemical Systems, Inc. Surface treatment for aluminum and aluminum alloys
US4422886A (en) * 1982-01-29 1983-12-27 Chemical Systems, Inc. Surface treatment for aluminum and aluminum alloys
US4470853A (en) * 1983-10-03 1984-09-11 Coral Chemical Company Coating compositions and method for the treatment of metal surfaces
GB2158845A (en) * 1984-05-18 1985-11-20 Parker Chemical Co Composition and process for treatment of ferrous substrates
US5129967A (en) * 1988-05-03 1992-07-14 Betz Laboratories, Inc. Composition and method for non-chromate coating of aluminum
US5143562A (en) * 1991-11-01 1992-09-01 Henkel Corporation Broadly applicable phosphate conversion coating composition and process
US5226976A (en) * 1991-04-15 1993-07-13 Henkel Corporation Metal treatment
US5282905A (en) * 1991-02-12 1994-02-01 Betz Laboratories, Inc. Method and composition for treatment of galvanized steel
US5328525A (en) * 1993-01-05 1994-07-12 Betz Laboratories, Inc. Method and composition for treatment of metals
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US5380374A (en) * 1993-10-15 1995-01-10 Circle-Prosco, Inc. Conversion coatings for metal surfaces
US5441580A (en) * 1993-10-15 1995-08-15 Circle-Prosco, Inc. Hydrophilic coatings for aluminum
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US20110217476A1 (en) * 2008-11-27 2011-09-08 Dingwerth Bjoern Conversion layers for surfaces containing zinc
US9273399B2 (en) 2013-03-15 2016-03-01 Ppg Industries Ohio, Inc. Pretreatment compositions and methods for coating a battery electrode
CN117107183A (zh) * 2023-08-30 2023-11-24 东风商用车有限公司 一种锌表面无铬钝化液及其应用

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DE2031358C3 (de) * 1970-06-25 1981-10-15 Gerhard Collardin GmbH, 5000 Köln Verfahren zur Erzeugung von Schutzschichten auf Aluminium, Eisen und Zink mittels saurer, komplexe Fluoride enthaltender, Lösungen
JPS5973316U (ja) * 1982-11-09 1984-05-18 小池　軍蔵 ネクタイ
JPS59165414U (ja) * 1983-04-16 1984-11-06 中路　善三 アツプリケをベ−ルで覆つたネクタイ
JPS60215772A (ja) * 1984-04-10 1985-10-29 Nippon Parkerizing Co Ltd アルミニウムおよびその合金の表面処理方法
US6720032B1 (en) 1997-09-10 2004-04-13 Henkel Kommanditgesellschaft Auf Aktien Pretreatment before painting of composite metal structures containing aluminum portions
DE19933189A1 (de) * 1999-07-15 2001-01-18 Henkel Kgaa Verfahren zur korrosionsschützenden Behandlung oder Nachbehandlung von Metalloberflächen
JP2008184690A (ja) * 2002-12-24 2008-08-14 Nippon Paint Co Ltd 塗装前処理方法
JP4526807B2 (ja) * 2002-12-24 2010-08-18 日本ペイント株式会社 塗装前処理方法
JP4989842B2 (ja) * 2002-12-24 2012-08-01 日本ペイント株式会社 塗装前処理方法
DE102005059314B4 (de) 2005-12-09 2018-11-22 Henkel Ag & Co. Kgaa Saure, chromfreie wässrige Lösung, deren Konzentrat, und ein Verfahren zur Korrosionsschutzbehandlung von Metalloberflächen
DE102007043479A1 (de) * 2007-09-12 2009-03-19 Valeo Schalter Und Sensoren Gmbh Verfahren zur Oberflächenbehandlung von Aluminium und ein Schichtaufbau eines Bauteils aus Aluminium mit einer elektrischen Kontaktierung
DE102007057185A1 (de) 2007-11-26 2009-05-28 Henkel Ag & Co. Kgaa Zirconiumphosphatierung von metallischen Bauteilen, insbesondere Eisen
BRPI0909501B1 (pt) 2008-03-17 2019-03-26 Henkel Ag & Co. Kgaa Método
DE102008014465B4 (de) 2008-03-17 2010-05-12 Henkel Ag & Co. Kgaa Mittel zur optimierten Passivierung auf Ti-/Zr-Basis für Metalloberflächen und Verfahren zur Konversionsbehandlung
JP5215043B2 (ja) * 2008-06-02 2013-06-19 日本パーカライジング株式会社 金属の表面処理用処理液及び表面処理方法
CA2784149C (en) 2009-12-28 2017-07-25 Henkel Ag & Co. Kgaa Metal pretreatment composition containing zirconium, copper, zinc, and nitrate and related coatings on metal substrates

Cited By (61)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3920486A (en) * 1973-05-10 1975-11-18 Oxy Metal Industries Corp Method of blackening ferrous metal surfaces
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ZA704412B (en) 1971-07-28
DE1933013B2 (de) 1977-12-29
DE1933013C3 (de) 1978-09-21
FR2051358A5 (enrdf_load_stackoverflow) 1971-04-02
BE752626A (fr) 1970-12-28
SE358422B (enrdf_load_stackoverflow) 1973-07-30
DE1933013A1 (de) 1971-01-07
NL7009376A (enrdf_load_stackoverflow) 1970-12-30
JPS4824618B1 (enrdf_load_stackoverflow) 1973-07-23
GB1316865A (en) 1973-05-16

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