EP0337411B1 - Procédé de préparation d'un bain acide pour passiver du zinc, des alliages de zinc et du cadmium, contenant du chrome III et un fluorure - Google Patents

Procédé de préparation d'un bain acide pour passiver du zinc, des alliages de zinc et du cadmium, contenant du chrome III et un fluorure Download PDF

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Publication number
EP0337411B1
EP0337411B1 EP89106447A EP89106447A EP0337411B1 EP 0337411 B1 EP0337411 B1 EP 0337411B1 EP 89106447 A EP89106447 A EP 89106447A EP 89106447 A EP89106447 A EP 89106447A EP 0337411 B1 EP0337411 B1 EP 0337411B1
Authority
EP
European Patent Office
Prior art keywords
fluoride
zinc
chromium
iii
acid
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
EP89106447A
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German (de)
English (en)
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EP0337411A3 (en
EP0337411A2 (fr
Inventor
Klaus-Peter Klos
Karl-Heinz Lindemann
Willi Birnstiel
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.)
Surtec GmbH
Original Assignee
Surtec GmbH
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Publication date
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Priority to DE8916143U priority Critical patent/DE8916143U1/de
Priority to AT89106447T priority patent/ATE97700T1/de
Publication of EP0337411A2 publication Critical patent/EP0337411A2/fr
Publication of EP0337411A3 publication Critical patent/EP0337411A3/de
Application granted granted Critical
Publication of EP0337411B1 publication Critical patent/EP0337411B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • C23C22/06—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
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium

Definitions

  • the invention relates to a method for producing an acidic chromium-containing and fluoride-containing passivation bath for zinc or cadmium surfaces.
  • an acidic chromium-containing passivation bath for zinc or cadmium surfaces is known from US Pat. No. 4,263,059 and DE-OS 30 38 699, which, in addition to a "blue solution" of trivalent chromium and an acid, such as formic, acetic or propionic acid or nitric, sulfuric, hydrochloric and hydrofluoric acid contains a fluoride with a "green solution" of hexavalent chromium, for example Chromium trioxide, alkali metal chromate and dichromate and a reducing agent such as an aldehyde or alcohol or an alkali metal sulfite, bisulfite, metabisulfite, iodide, hydrogen peroxide, sulfur dioxide or an iron (II) salt is formed.
  • a fluoride with a "green solution” of hexavalent chromium for example Chromium trioxide, alkali metal chromate and dichromate and a reducing
  • surfaces made of zinc, zinc alloys, galvanically or by hot-dip galvanizing on iron or steel or zinc layers or cadmium surfaces are made more corrosion-resistant, which is indicated by a coloration that ranges from blue to black and yellow to olive and is also used for decorative purposes.
  • a passivation for example, the so-called blue passivation, ie Generation of a light blue, very thin passivation layer with a good decorative appearance, formation of zinc corrosion products also called "white rust", greatly delayed.
  • the salt spray test according to DIN 50021 provides a measure of the corrosion protection of these chromates.
  • a zinc-coated and passivated part is exposed to a 5% sodium chloride mist at 40 ° C and 100% humidity. The time required to oxidize 5 - 10% of the surface to white rust is then given.
  • the corrosion protection according to DIN 50021 should be 20 to 24 hours.
  • Chromium (III) fluorine complexes of chromium (III) are known, the formation of which is accelerated by zinc, but there is no evidence of the blue passivation of zinc or galvanized in this investigation of equilibrium constants Iron surfaces, on where there is no chrome metal deposition, but a polymeric compound with divalent chromium is deposited.
  • This object is achieved according to the invention by a process for producing an acidic, chromium (III) -containing and fluoride-containing passivation bath for surfaces made of zinc, zinc alloys and cadmium by mixing 20 to 200 g / l of a soluble chromium (111) compound 20 to 600 g / l of a soluble nitrate (total nitrate) 5 to 100 g / l of a fluoride and hydrochloric or nitric acid to a pH of 1.8 to 2.2 and an anion selected from the group consisting of sulfate, phosphate, chloride, bromide, fluoride and iodide, the soluble nitrate in greater concentration than the chromium (III ) Concentration (in g / l) is present, and the mixture is either heated to 60 ° C.
  • the concentrate obtained is optionally brought to an application concentration of 2 to 20% by weight in water , dissolved, which is characterized in that it additionally contains an acidic ion exchanger loaded with Cr3+ and / or an agent for the insolubilization of Fe3+ ions in an amount of 0.1 to 100 g / l.
  • a catalyst in particular with activated carbon at 15 ° C. or above, for example at room temperature (20-25 ° C.) or brief heating, for example 30 seconds to 15 minutes. to at least 60 to 80 ° C, seems to promote the formation of the more stable chromium (III) complexes, which is surprising is because only the hexahydrate complexes of chromium are stable at room temperature, but they are unusable for passivation.
  • Passivation baths preferred according to the invention contain the following amounts in a concentrate which is usually used in a concentration of 2 to 20% by weight in water: 20-200 g / l chromium (III) compound, e.g. as chromium chloride or chromium nitrate, 20 - 600 g / l soluble nitrate, such as sodium, potassium or ammonium nitrate, 5 - 100 g / l fluoride, e.g. sodium, potassium, ammonium fluoride Hydrochloric or nitric acid up to a pH of 1.8 to 2.2.
  • a concentrate which is usually used in a concentration of 2 to 20% by weight in water: 20-200 g / l chromium (III) compound, e.g. as chromium chloride or chromium nitrate, 20 - 600 g / l soluble nitrate, such as sodium, potassium or ammonium nitrate, 5 - 100
  • Passivation baths made from this concentrate show corrosion protection values of a blue passivation according to DIN 50021 from 44 to 50 h, the layers can be colored and good organic polymers are applied to the layers.
  • a concentrate of the following composition was produced: 50 g / l chromium (III) chloride 125 g / l sodium nitrate 50 g / l sodium fluoride
  • the concentrate was heated to 65 ° C. It contained complexes of the formula
  • the bath was mixed with water in a weight ratio of 1:10 and adjusted to pH 2.0 with nitric acid. With this bath, hot-dip galvanized iron bars of 2 cm in diameter and 20 cm in length were blue passivated. After 3 seconds, the rods were removed from the bath and checked for corrosion behavior in accordance with DIN 50021. The corrosion protection value was 48 hours.
  • the durability of the bath was extended by a factor of 10 by adding 50 g / l of acetylacetone.
  • a bath was out 60 g / l Cr (NO3) 3.9H2O 100 g / l NaNO3 40 g / l NaF HNO3 ad pH 2.1 and without heating, but prepared by treating with granular activated carbon in a porous bag for 10 minutes and, after mixing with water in a weight ratio of 1:12, used for the same experiment. It contained complexes of the formula The same corrosion protection value was obtained.
  • the following results were obtained in a comparison test on normal blue chromating (commercially available): with Cr VI (commercially available): 15 mg Cr / m2 zinc; 24 h corrosion protection Cr III (according to the invention: 30 mg Cr / m2 zinc; 48 h corrosion protection.
  • the durability of the bath was extended by a factor of 5 by adding 20 g / l salicylic acid.
  • the bath with the ion exchanger showed a perfect blue passivation, while the comparison bath was unusable after a short time.
  • the addition of 10 g / l fumaric acid increases the life of the bath by a factor of 5.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Chemically Coating (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Glass Compositions (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Claims (2)

  1. Procédé pour la préparation d'un bain acide de passivation contenant du chrome-(III) et un fluorure, pour surfaces de zinc, cadmium et alliages de zinc, par mélangeage de
       20 à 200 g/l d'un composé de chromique soluble,
       20 à 600 g/l d'un nitrate soluble (nitrate total),
       5 à 100 g/l d'un fluorure, et de l'acide chlorhydrique ou nitrique jusqll'à un pH de 1,8 à 2,2, ainsi qu'un anion, choisi parmi les anions sulfate, phosphate, chlorure, bromure, fluorure et iodure, le nitrate soluble étant présent à une concentration supérieure à la concentration du chrome-(III) (en g/l), et soit chauffage du mélange à 60°C, soit traitement de celui-ci par un catalyseur au-dessus de 15°C, et le concentré obtenu est éventuellement porté à une concentration d'utilisation de 2 à 20 % en poids dans de l'eau, caractérisé en ce que l'on ajoute en plus un échangeur d'ions chargé de Cr³⁺ et/ou un agent pour l'insolubilisation d'ions Fe³⁺, en une quantité de 0,1 à 100 g/l.
  2. Procédé selon la revendication 1, caractérisé en ce que l'agent pour l'insolubilisation des ions Fe³⁺ est choisi parmi l'acétylacétone, l'acide fumarique, l'acide gluconique, l'acide oxalique, l'acide lactique, des amines cycliques et alicycliques, primaires ou secondaires, des aminoacides et des amides, ayant de 3 à 16 atomes de carbone, qui forment avec des ions ferriques des composés insolubles ou peu solubles dans l'eau.
EP89106447A 1988-04-12 1989-04-11 Procédé de préparation d'un bain acide pour passiver du zinc, des alliages de zinc et du cadmium, contenant du chrome III et un fluorure Expired - Lifetime EP0337411B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE8916143U DE8916143U1 (de) 1988-04-12 1989-04-11 Saures chrom-(III)-haltiges und fluoridhaltiges Passivierungsbad-Konzentrat für Oberflächen aus Zink, Zinklegierungen und Cadmium
AT89106447T ATE97700T1 (de) 1988-04-12 1989-04-11 Verfahren zur herstellung eines sauren chrom(iii)-haltigen und fluoridhaltigen passivierungsbades fuer oberflaechen aus zink, zinklegierungen und cadmium.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3812076 1988-04-12
DE3812076A DE3812076A1 (de) 1988-04-12 1988-04-12 Saures chrom-(iii)-haltiges und fluoridhaltiges passivierungsbad fuer oberflaechen aus zink, zinklegierungen und cadmium

Publications (3)

Publication Number Publication Date
EP0337411A2 EP0337411A2 (fr) 1989-10-18
EP0337411A3 EP0337411A3 (en) 1990-05-09
EP0337411B1 true EP0337411B1 (fr) 1993-11-24

Family

ID=6351774

Family Applications (1)

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EP89106447A Expired - Lifetime EP0337411B1 (fr) 1988-04-12 1989-04-11 Procédé de préparation d'un bain acide pour passiver du zinc, des alliages de zinc et du cadmium, contenant du chrome III et un fluorure

Country Status (5)

Country Link
EP (1) EP0337411B1 (fr)
AT (1) ATE97700T1 (fr)
DD (1) DD280557A5 (fr)
DE (2) DE3812076A1 (fr)
YU (1) YU71689A (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6946201B2 (en) 1996-04-19 2005-09-20 Surtec International Gmbh Chromium (VI)-free conversion layer and method for producing it
CN102912337A (zh) * 2012-10-30 2013-02-06 四川华丰企业集团有限公司 一种镀镉工件的绿色钝化膜生产工艺

Families Citing this family (14)

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DE4135524C2 (de) * 1991-10-28 1995-01-26 Gc Galvano Consult Gmbh Verfahren und Mittel zum Chromatieren von Oberflächen aus Zink oder Cadmium oder Legierungen davon
US7314671B1 (en) 1996-04-19 2008-01-01 Surtec International Gmbh Chromium(VI)-free conversion layer and method for producing it
JP4145016B2 (ja) * 2001-01-31 2008-09-03 日本パーカライジング株式会社 亜鉛系メッキ鋼板用防錆処理剤および亜鉛系メッキ鋼板
US6761774B2 (en) * 2001-05-24 2004-07-13 Basf Corporation Composition and method for the in situ removal scale from a substrate
US7101469B2 (en) 2004-11-10 2006-09-05 Atotech Deutschland Gmbh Metal pieces and articles having improved corrosion resistance
DE102009042861B4 (de) 2009-09-24 2020-08-20 AnJo Oberflächentechnik GmbH Zusammensetzung, Anwendungslösung und Verfahren zur Passivierung von Zink und seinen Legierungen
WO2011127473A1 (fr) * 2010-04-09 2011-10-13 Enthone Inc. Traitement de passivation de revêtements à base de zinc
DE102011013319B4 (de) 2011-03-07 2018-06-14 AnJo Oberflächentechnik GmbH Zusammensetzung und Anwendungslösung zum Passivieren von Zink und seinen Legierungen
EP2708620A1 (fr) 2012-09-12 2014-03-19 Anjo Oberflächentechnik GmbH Composition et solution destinées à la passivation du zinc et ses alliages
CN103215580B (zh) * 2013-03-25 2016-01-27 沈阳帕卡濑精有限总公司 用于钢板表面快速成膜具有高耐蚀性的三价铬钝化剂
CN103215581B (zh) * 2013-03-25 2015-06-03 沈阳帕卡濑精有限总公司 快速处理钢板表面钝化封闭一体的三价铬钝化剂
ES2732264T3 (es) * 2014-02-13 2019-11-21 Doerken Ewald Ag Procedimiento para la preparación de un sustrato provisto de una pasivación libre de cobalto y libre de cromo-VI
NL2017398B1 (en) * 2016-08-31 2018-03-08 Ad Productions B V Method of treating metal surfaces with an aqueous composition and aqueous composition
US10400338B2 (en) 2017-05-12 2019-09-03 Chemeon Surface Technology, Llc pH stable trivalent chromium coating solutions

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DE2166737A1 (de) * 1970-04-02 1975-06-05 Du Pont Verfahren zum herstellen von chromhaltigen, waessrigen loesungen
US4171231A (en) * 1978-04-27 1979-10-16 R. O. Hull & Company, Inc. Coating solutions of trivalent chromium for coating zinc surfaces
US4298404A (en) * 1979-09-06 1981-11-03 Richardson Chemical Company Chromium-free or low-chromium metal surface passivation
US4263059A (en) * 1979-12-21 1981-04-21 Rohco, Inc. Coating solutions of trivalent chromium for coating zinc and cadmium surfaces
CA1228000A (fr) * 1981-04-16 1987-10-13 David E. Crotty Solution et procede de passivation, donnant un aspect chrome
US4384902A (en) * 1981-06-15 1983-05-24 Occidental Chemical Corporation Trivalent chromium passivate composition and process
US4359347A (en) * 1981-04-16 1982-11-16 Occidental Chemical Corporation Chromium-free passivate solution and process
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US4539348A (en) * 1982-12-16 1985-09-03 Celanese Corporation Water-swellable crosslinked polymeric microgel particles and aqueous dispersions of organic film-forming resins containing the same
US4578122A (en) * 1984-11-14 1986-03-25 Omi International Corporation Non-peroxide trivalent chromium passivate composition and process
NO168953C (no) * 1986-08-27 1992-04-22 Elektro Brite Gmbh Surt kromholdig passiveringsbad for sink- eller kadmiumoverflater

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6946201B2 (en) 1996-04-19 2005-09-20 Surtec International Gmbh Chromium (VI)-free conversion layer and method for producing it
CN102912337A (zh) * 2012-10-30 2013-02-06 四川华丰企业集团有限公司 一种镀镉工件的绿色钝化膜生产工艺
CN102912337B (zh) * 2012-10-30 2015-01-21 四川华丰企业集团有限公司 一种镀镉工件的绿色钝化膜生产工艺

Also Published As

Publication number Publication date
YU71689A (en) 1990-12-31
DE3812076C2 (fr) 1990-09-13
DD280557A5 (de) 1990-07-11
DE3812076A1 (de) 1989-10-26
DE58906227D1 (de) 1994-01-05
EP0337411A3 (en) 1990-05-09
EP0337411A2 (fr) 1989-10-18
ATE97700T1 (de) 1993-12-15

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