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WO1994023089A1 - Composition et procede de substitution pour le placage de surfaces zinciferes - Google Patents

Composition et procede de substitution pour le placage de surfaces zinciferes Download PDF

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Publication number
WO1994023089A1
WO1994023089A1 PCT/US1994/003225 US9403225W WO9423089A1 WO 1994023089 A1 WO1994023089 A1 WO 1994023089A1 US 9403225 W US9403225 W US 9403225W WO 9423089 A1 WO9423089 A1 WO 9423089A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
zinciferous
heavy metal
plating
sheet
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/US1994/003225
Other languages
English (en)
Inventor
Noriaki Yoshitake
Yoshiyuki Murasawa
Shotaro Tsuda
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.)
Henkel Corp
Original Assignee
Henkel Corp
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 Corp filed Critical Henkel Corp
Priority to DE69411902T priority Critical patent/DE69411902T2/de
Priority to US08/537,753 priority patent/US5624480A/en
Priority to EP94913306A priority patent/EP0693139B1/fr
Publication of WO1994023089A1 publication Critical patent/WO1994023089A1/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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • 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
    • C23C22/78—Pretreatment of the material to be coated

Definitions

  • the present invention relates to an acidic substitutional plating bath compo ⁇ sition, also called a "bath" herein for brevity, for application to zinciferous surfaces, particularly to steel sheet plated with zinc-containing metal (hereinafter referred to as zinciferous metal-plated steel sheet), and to processes for using such a compo ⁇ sition to treat metals. More specifically, the present invention relates to an acidic substitutional plating bath composition that can be continuously employed for long periods of time while maintaining its initial performance and that, upon contact with the surface of zinciferous metal-plated steel sheet, forms thereon a heavy metal film that contributes to the formation of a paint undercoat that is very strongly ad ⁇ herent for paint films. This acidic substitutional plating bath composition can also improve the black rust resistance of the unpainted sheet.
  • zinciferous metal-plated steel sheet encompass ⁇ es steel sheet plated with zinc or a zinc alloy.
  • Said zinc alloys encompass, for example, zinc-aluminum alloys, zinc-nickel alloys, and zinc-iron alloys.
  • low-lead hot-dip galvanized steel sheet (with a lead content in the zinc plating layer reduced from that in conventional hot-dip galvanized steel sheet), it has already been discovered that corrosion inhibition is obtained due to the absence of lead segregation at the grain boundaries of the crystals in the plat ⁇ ing layer and at the interface between the plating layer and alloy layer.
  • Low-lead hot-dip galvanized steel sheet is, as a consequence, widely used in various industri ⁇ al sectors.
  • low-lead hot-dip galvanized steel sheet resists cracking during bending processes, with the result that shear stresses become concentrated in the phosphate film posi ⁇ tioned between the steel sheet and paint film. This produces cohesive failure in the phosphate film, which in turn causes facile delamination of the paint film.
  • Japanese Patent Publication Num- ber Sho 43-12974 relates to a method in which zinciferous metal-plated steel sheet is treated with a basic aqueous solution (pH > 11) containing Co 2 ⁇ Fe 2+ , Fe 3+ , or Ni 2+ prior to execution of a chromate treatment on the sheet.
  • a basic aqueous solution pH > 11
  • Co 2 ⁇ Fe 2+ , Fe 3+ , or Ni 2+ prior to execution of a chromate treatment on the sheet.
  • large amounts of sludge are produced in this method due to the accumulation of the zinc ion eluting into the treatment bath with elapsed treatment time. This necessitates a sludge removal step, which impairs the workability.
  • (2) Japanese Patent Publication Number Sho 52-22618 and (3) Japanese Patent Publication Number Sho 52-43171 relate to methods in which galvanized steel sheet is treated with an acidic solution (pH around 1.5) that contains Ni 2+ , Co + , Fe 2+ , and/or Fe 3+ prior to execution of a chromate treatment on the sheet.
  • the acidic substitutional plating baths dis ⁇ closed in (2) Japanese Patent Publication Number Sho 52-22618 and (3) Japan- ese Patent Publication Number Sho 52-43171 contain an inorganic acid such as hydrochloric acid, sulfuric acid, hydrofluoric acid, or fluosilicic acid, or an organic acid such as citric acid, acetic acid, oxalic acid, and so forth.
  • the zinc ion eluted into the plating bath is present in dissolved form through the formation of a salt with the inorganic acids or through complex formation with the organic acids.
  • the pH in substitutional plating baths of this type is readily increased by the increase in zinc ion concentration, which results in a decline in the substitutional plating re ⁇ actions. Due to this, large quantities of inorganic acid must be added in order to maintain the pH of the plating bath at the desired values, and this facilitates corro ⁇ sion of, for example, stainless steel plating bath tanks, pipes, and so forth. There- fore such baths are quite difficult to implement on a practical basis without the use of a stainless steel reactor and piping both coated with rubber lining or the like. This use of corrosive acid, particularly a volatile one such as hydrochloric acid, also causes a deterioration in the working environment.
  • Japanese Patent Application Laid Open Number Sho 61-69978 concerns a method in with low-lead hot-dip galvanized steel sheet is treated with an aqueous alkaline solution that contains Fe, Co, and/or Ni or with an aqueous hydrochloric acid solution, aqueous sulfuric acid solution, or aqueous phosphoric acid solution that contains Fe, Co, and/or Ni.
  • aqueous hydro ⁇ chloric acid solution, aqueous sulfuric acid solution, and aqueous alkaline solution deposition of these metals is impaired by the increase in Zn ion and increase in pH that occur with elapsed treatment time.
  • black rust inhibition is achieved by the pre-chromating treatment of zincif ⁇ erous metal-plated steel sheet with a treatment bath that has a pH of 1 to 4 or 11 to 13.5 and that contains Ni 2+ ion or Co 2+ ion. Even this method, however, suffers from a reduced workability due to the production of sludge that occurs when the zinc ion concentration becomes elevated during the course of treatment. Disclosure of the Invention
  • the present invention seeks to introduce a very generally applicable acidic bath composition for the substitutional plating of zinciferous metal-plated steel sheet that is almost free of equipment corrosion and that is capable of a very efficient deposition of heavy metal (e.g., Ni, Co, and/ or Fe, etc.) on zinciferous metal-plated steel sheet, with no sludge production with elapsed treatment time, despite the increased zinc ion concentrations in the substi ⁇ tutional plating bath.
  • heavy metal e.g., Ni, Co, and/ or Fe, etc.
  • the acidic substitutional plating bath composition of the present invention for application to zinciferous metal-plated steel sheet character- istically has a pH of 2.0 to 4.5 and contains 1.5 to 40 g/L as metal atoms of at least one heavy metal ion selected from nickel, iron, and cobalt; 0.5 to 10 g/L of phosphate ions, including the stoichiometric equivalent as phosphate ions of any undissociated phosphoric acid present in the solution and of all the anions other than phosphate itself produced by any degree of dissociation of phosphoric acid; 1 to 250 g/L of sulfate ions; and 1 to 20 g/L of organic acid.
  • the inventors have discovered that when phosphoric acid with its high pH buffering capacity is used in the acidic substitutional plating bath in place of the aforesaid inorganic acids, the pH variations are relaxed despite the increases in the zinc ion concentration, and the amount of free inorganic acid ion can therefore be restrained.
  • This makes possible the preparation of an acidic substitutional plat ⁇ ing bath that solves the problem with prior acidic substitutional plating baths through its almost complete lack of corrosiveness for stainless steel containers and piping.
  • the plating baths disclosed in the prior-art examples referenced above contain compounds of antimony, tin, and so forth, in order to prevent a de ⁇ cline in the substitutional plating reactions at increased levels of zinc ion.
  • the acidic substitutional plating bath in accordance with the present in ⁇ vention must contain the following components:
  • the bath must contain at least one heavy metal ion selected from nick ⁇ el, iron, and cobalt.
  • heavy metal ion selected from nick ⁇ el, iron, and cobalt.
  • These are advantageously supplied to the plating bath in the form of the corresponding sulfates, phosphates, carbonates, oxides, hydroxides, and organic acid salts.
  • nitrate is undesirable because its presence can lead to the formation of a phosphate film upon zinc dissolution.
  • long- term use of the chloride runs the risk of chloride ion accumulation and corrosion of the plating equipment.
  • the plating bath should contain said heavy metal ion(s) at 1.5 to 40 g/L cal ⁇ culated as metal atoms. Metal deposition is inadequate at below 1.5 g/L and a satisfactory effect is therefore not obtained. At above 40 g/L, on the other hand, 5 metal deposition is saturated and the economic losses due to bath carry-out be ⁇ come large.
  • Orthophosphoric acid is preferably used as the source for the phosphate ion used by the present invention.
  • the content of phosphoric acid in the plating bath should be 0.5 to 10 g/L as phosphate ion.
  • the use of less than 0.5 g/L will o result in a sharp increase in bath pH, which influences the component balance.
  • the pH buffering activity is substantially saturated at above 10 g/L, while the amount of zinc etching is increased, with a corresponding decline in deposition ef ⁇ ficiency.
  • Sulfate ions in the present invention are preferably supplied by sulfuric acid. s Its content gradually increases because it is generated — by zinc ion capture — in correspondence to the increase in zinc ion. Accordingly, the sulfate ion concen ⁇ tration should be determined by the amount of zinc etching and the amount of plat ⁇ ing bath carry-out, but must generally fall in the range of 1 to 250 g/L. Capture of the eluted zinc ion is inadequate at below 1 g/L, while exceeding 250 g/L is eco- o nomically unattractive because the effect is saturated at such levels.
  • the organic acid used by the present invention comprises at least one se ⁇ lection from glycolic acid, lactic acid, malic acid, tartaric acid, citric acid, gluconic acid, and ascorbic acid.
  • the organic acid is citric or malic acid.
  • the organic acid concentration should be 1 to 20 g/L. Both the ability to capture eluted 5 zinc and the pH buffering capacity are inadequate when the organic acid concen ⁇ tration is less than 1 g/L. On the other hand, the effect becomes saturated when the organic acid concentration exceeds 20 g/L, and these high concentrations also impair the heavy metal deposition efficiency.
  • An acidic substitutional plating bath in accordance with the present inven- o tion containing the ingredients as described above should have a pH adjusted into the range of 2.0 to 4.5.
  • the pH value may be maintained in this range through the supplementary addition of hydrofluoric acid or fluosilicic acid to the plating bath.
  • Zinc oxide or ammonia can be added when the pH is too low.
  • the reasons for the restriction to the pH range of 2.0 to 4.5 are as follows: a pH below 2 signifies an excessive content of inorganic acid, which results in too much zinc etching; equip ⁇ ment corrosion also becomes a risk at lower pH values; at pH values in excess of 4.5 the substitutional plating reactivity is impaired when the amount of eluted zinc ion has become increased.
  • Acidic substitutional plating may be run by bringing the surface of the zincif ⁇ erous metal-plated steel sheet into contact with the acidic substitutional plating bath by spraying, immersion, coating, and so forth. Plating is thereby conducted to the desired degree, and is followed by a water wash and drying.
  • the tempera ⁇ ture of the plating bath should be room temperature to 80 * C, and a treatment time of less than 1 minute will be sufficient. Insofar as concerns the amount of heavy metal deposition, 1 to 100 mg/m 2 can provide a desirable performance in the case of paint undercoating treatments, while 0.3 to 20 mg/m 2 can provide a desirable black rust prevention in the case of anticorrosion chromate treatments.
  • de ⁇ sired effects may not appear when the amount of heavy metal does not meet these lower limits, while exceeding the upper limits is economically unattractive be ⁇ cause no additional improvement in performance is obtained above the upper lim ⁇ its. Simply driving off the water is sufficient for drying, and the sheet temperature in drying will generally fall in the range of 50' C to 100' C.
  • the substitutional plating bath in accordance with the present invention may be applied to the surface of pure zinc, hot-dip galvanization, hot-dip galvanization that contains aluminum or iron as alloying components, and steel sheet electroplat ⁇ ed with zinc or zinciferous metal.
  • the zinciferous metal-plated steel sheet is typically subjected to an application-type chromate treat ⁇ ment for the purpose of improving the corrosion resistance, and this is followed by painting.
  • the execution of the subject surface treatment imparts a microscopically etched texture to the surface of the zinciferous metal-plated steel sheet, which has an anchoring effect on the paint film.
  • Examples Examples 1 to 3 and Comparison Examples 1 to 4 In each of Examples 1 to 3 and Comparison Examples 1 to 3, the test sheets [as described in General Condition (1 ) below] were substitutionaliy plated using a treatment bath with the composition reported in Table 1. The organic acid was citric acid in Examples 1 - 6 and malic acid in Examples 7 - 12. The substitu ⁇ tionaliy plated test sheets and test sheet without substitutional plating (Comparison Example 4) were then cleaned, dried, chromated, and painted in this sequence as described in (3) through (6) below. The painted test sheets were subsequently submitted to flexural testing and corrosion resistance testing as described in (7) and (8) below.
  • Table 2 reports the following values: the substitutional plating con ⁇ ditions, the presence/absence of sludge production and the amount of zinc ion in the bath for treatment bath into which zinc ion has been dissolved by the continu ⁇ ous treatment of test sheets, the amount of heavy metal deposition by substitution ⁇ al plating, and the results of flexural testing and corrosion resistance testing on the painted sheet.
  • CTR corrosion resistance test results for painted, treated sheets
  • Se c secc >nds of treatment time
  • NA no abnormalities.
  • Corrosion resistance testing of the painted sheet A 70 x 150 mm coupon was cut from each test sheet and subjected to the salt-spray test stipulated in JIS Z 2371 for 500 hours. Blistering on the surface of the painted cou- o pon was then evaluated according to the criteria of the American Society for Testing and Materials (ASTM).
  • test sheets as re ⁇ ported in (1) below were subjected to substitutional plating treatments using the treatment bath compositions reported in Table 3.
  • the substitutionally plated test 5 sheets and test sheet without substitutional plating (Comparison Example 8) were then cleaned, dried, chromated, and painted in this sequence as described in (3) through (6) below.
  • Comparison Example 7 the test sheet was treated with zinc phosphate and then painted. The painted test sheets were subsequently submit ⁇ ted to flexural testing and edge creepage testing as described in (7) and (8) below.
  • Table 4 reports the following values: the substitutional plating conditions, the pres ⁇ ence/absence of sludge production and the amount of zinc ion in the bath for treat ⁇ ment bath into which zinc ion has been dissolved by the continuous treatment of test sheet, the amount of heavy metal deposition by substitutional plating, and the results of flexural testing and edge creepage testing on the painted sheet.
  • Edge creepage test on the painted sheet 70 x 150 mm coupons were cut from the test sheets in such a way that fins projected out at the top and bottom on both ends. After 1000 hours of salt-spray testing in accordance with JIS Z 2371 , the maximum creepage widths (mm) from the edges were measured on both sides. The average value is reported.
  • test sheets as re ⁇ ported in (1) below were subjected to substitutional plating treatments using the treatment bath compositions reported in Table 5.
  • the substitutionally plated test sheets and test sheet without substitutional plating (Comparison Example 11 ) were then degreased, cleaned, dried, chromated, and painted in this sequence as de ⁇ scribed in (2) through (9) below.
  • the thus-treated test sheets were subsequently submitted to adherence testing on the painted sheet and corrosion resistance test- ing on the painted sheet as described in (10) and (11) below.
  • Table 6 reports the following values: the substitutional plating conditions, the presence/absence of sludge production and the amount of zinc ion in the bath for treatment bath into Table 5
  • Chromate treatment An application-type chromate bath (aqueous disper ⁇ sion containing 2 % Cr 6* and 1 % Cr 3* ) was roll coated so as to give a chromium add-on of 50 mg/m 2 , followed by drying in a 250' C hot-air drying oven at a maximum attained sheet temperature of 150' C.
  • Adherence testing of the painted sheet 1.
  • Checkerboard test Using a cutter, a grid of 1 mm x 1 mm squares was cut into the test sheet to the basis metal; the extent of peeling of the paint film was evaluated after peeling with tape; 2.
  • test sheets as reported in (1) below were subjected to substitutional plating treatments using the treatment bath compositions reported in Table 7.
  • the substitutionally plated test sheets and test sheet without substitutional plating (Comparison Example 14) were then cleaned, dried, and chromated in this sequence as described in (3) through (5) below.
  • the thus-treated test sheets were subsequently submitted to accelerat ⁇ ed white rust testing and accelerated black rust testing as described in (6) and (7) below.
  • Table 8 reports the following values: the substitutional plating conditions, the presence/absence of sludge production and the amount of zinc ion in the bath for treatment bath into which zinc ion has been dissolved by the continuous treat ⁇ ment of test sheet, the amount of heavy metal deposition by substitutional plating, and the results of accelerated white rust testing and accelerated black rust testing.
  • Accelerated white rust testing A 70 x 150 mm test coupon was cut from the test sheet and subjected to salt-spray testing in accordance with JIS Z 2371. The area of white rust development was visually rated after 72 hours using the following criteria: 5: no white rust; 4: area of white rust develop ⁇ ment less than 5 %; 3: area of white rust development from 5 % to less than 25 %; 2: area of white rust development from 25 % to less than 50 %; 1 : area of white rust development is at least 50 %.
  • Accelerated black rust testing A multiple number of 70 x 150 mm coupons were cut from the test sheet.
  • Pairs were prepared by placing the test sur ⁇ faces of the coupons against one another, and these pairs were stacked. The entire assembly was wrapped with vinyl-coated paper, and the four cor ⁇ ners of the assembly were tightened down with bolts. A load of 1 kgf/cm 2 was applied using a torque wrench. The assembly was held for 240 hours in a humidifying tester at 49 ° C and 98 % relative humidity and subsequent ⁇ ly withdrawn. Blackening of the overlaid regions was then visually rated using the following criteria: 5: no blackening; 4: very slight greying; 3: less than 25 % blackening; 2: blackening from 25 % to less than 50 %; 1 : blackening at least 50 %.
  • the acidic substitutional plating bath composition of the invention for zinciferous metal-plated steel sheet imparts an excellent adherence and corrosion resistance to the painted sheet.
  • this composition yields an excellent black rust resistance.
  • the acidic substitutional plating bath composition of the invention retains its initial performance for long periods of time and can therefore be used on a continuous basis. Finally, it is almost completely free of corrosiveness for equipment. As a result of these attributes, the invention composition has substantial industrial usefulness.

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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)
  • Chemically Coating (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

Bain électrolytique acide de substitution pour surface zincifères et plus particulièrement pour tôles à revêtement metallique zincifère inhibant la formation de boues et améliorant le rendement du dépôt d'ions metalliques lourds, et consistant en une composition aqueuse d'un pH compris entre 2 et 4.5 contenant entre 1.5 et 40g/L d'au moins un ion métal lourd choisi parmi le nickel, le fer ou le cobalt; 0.5 à 10 g/L d'ions phosphate; 1 à 250 g/L d'ions sulfate et de 1 à 20 g/L d'un acide organique.
PCT/US1994/003225 1993-04-07 1994-03-28 Composition et procede de substitution pour le placage de surfaces zinciferes Ceased WO1994023089A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE69411902T DE69411902T2 (de) 1993-04-07 1994-03-28 Zusammensetzung und verfahren zum substituierten plattieren von zink- oder zink-legierungs-oberflächen
US08/537,753 US5624480A (en) 1993-04-07 1994-03-28 Composition and process for substitutionally plating zinciferous surfaces
EP94913306A EP0693139B1 (fr) 1993-04-07 1994-03-28 Composition et procede de substitution pour le placage de surfaces de zinc ou d'alliages de zinc

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP5080883A JP2968147B2 (ja) 1993-04-07 1993-04-07 亜鉛含有金属めっき鋼板用酸性置換めっき液組成物
JP5/80883 1993-04-07

Publications (1)

Publication Number Publication Date
WO1994023089A1 true WO1994023089A1 (fr) 1994-10-13

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Application Number Title Priority Date Filing Date
PCT/US1994/003225 Ceased WO1994023089A1 (fr) 1993-04-07 1994-03-28 Composition et procede de substitution pour le placage de surfaces zinciferes

Country Status (8)

Country Link
EP (1) EP0693139B1 (fr)
JP (1) JP2968147B2 (fr)
CN (1) CN1065574C (fr)
AT (1) ATE168728T1 (fr)
CA (1) CA2158856A1 (fr)
DE (1) DE69411902T2 (fr)
TW (1) TW301675B (fr)
WO (1) WO1994023089A1 (fr)

Cited By (1)

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Publication number Priority date Publication date Assignee Title
EP1916317A1 (fr) * 2006-10-27 2008-04-30 Seppeler Holding und Verwaltungs GmbH & Co. KG Procédé de vieillissement prématuré de pièces métalliques dotées d'une surface essentiellement constituée de zinc

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Publication number Priority date Publication date Assignee Title
JP5463609B2 (ja) * 2005-03-31 2014-04-09 Ｊｆｅスチール株式会社 クロムフリー表面処理亜鉛系めっき鋼板およびその製造方法ならびに表面処理液
JP2007023353A (ja) * 2005-07-19 2007-02-01 Yuken Industry Co Ltd 亜鉛系めっき部材のノンクロム反応型化成処理
DE102007021364A1 (de) * 2007-05-04 2008-11-06 Henkel Ag & Co. Kgaa Metallisierende Vorbehandlung von Zinkoberflächen
CN101311308B (zh) * 2007-05-24 2011-04-27 西北工业大学 玻璃纤维表面化学镀五元合金镀液及其制备方法
WO2012036203A1 (fr) 2010-09-15 2012-03-22 Ｊｆｅスチール株式会社 Tôle d'acier pour conteneurs et son procédé de fabrication
DE102014223169A1 (de) * 2014-11-13 2016-05-19 Henkel Ag & Co. Kgaa Verfahren zur selektiven Entfernung von Zink-Ionen aus alkalischen Badlösungen in der Oberflächenbehandlung von metallischen Bauteilen in Serie

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US4486233A (en) * 1982-07-30 1984-12-04 Office National D'etudes Et De Recherche Aerospatiales Nickel and/or cobalt chemical plating bath using a reducing agent based on boron or phosphorous
US4636255A (en) * 1984-05-24 1987-01-13 Aisin Seiki Kabushiki Kaisha Electroless plating bath for forming a nickel alloy coating having a high phosphorus content
US4670066A (en) * 1984-08-16 1987-06-02 Compagnie Francaise De Produits Industriels Process for the treatment by chemical conversion of substrates of zinc or of one of its alloys, concentrate and bath used for performing this process
US4776898A (en) * 1985-03-20 1988-10-11 Omi International Corporation Passivation
US5185076A (en) * 1990-05-07 1993-02-09 C. Uyemura & Co., Ltd. Bath and method for electrodepositing tin, lead and tin-lead alloy
US5258061A (en) * 1992-11-20 1993-11-02 Monsanto Company Electroless nickel plating baths

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FR2654440B1 (fr) * 1989-11-16 1993-07-30 Produits Ind Cie Fse Procede de conversion chimique de substrats metalliques, bain mis en óoeuvre dans ce procede et concentre pour la preparation du bain.

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US3515600A (en) * 1966-10-19 1970-06-02 Hooker Chemical Corp Metal treating process and composition
US4486233A (en) * 1982-07-30 1984-12-04 Office National D'etudes Et De Recherche Aerospatiales Nickel and/or cobalt chemical plating bath using a reducing agent based on boron or phosphorous
US4636255A (en) * 1984-05-24 1987-01-13 Aisin Seiki Kabushiki Kaisha Electroless plating bath for forming a nickel alloy coating having a high phosphorus content
US4670066A (en) * 1984-08-16 1987-06-02 Compagnie Francaise De Produits Industriels Process for the treatment by chemical conversion of substrates of zinc or of one of its alloys, concentrate and bath used for performing this process
US4776898A (en) * 1985-03-20 1988-10-11 Omi International Corporation Passivation
US5185076A (en) * 1990-05-07 1993-02-09 C. Uyemura & Co., Ltd. Bath and method for electrodepositing tin, lead and tin-lead alloy
US5258061A (en) * 1992-11-20 1993-11-02 Monsanto Company Electroless nickel plating baths

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1916317A1 (fr) * 2006-10-27 2008-04-30 Seppeler Holding und Verwaltungs GmbH & Co. KG Procédé de vieillissement prématuré de pièces métalliques dotées d'une surface essentiellement constituée de zinc

Also Published As

Publication number Publication date
CN1065574C (zh) 2001-05-09
EP0693139A4 (fr) 1996-02-07
ATE168728T1 (de) 1998-08-15
JPH06293973A (ja) 1994-10-21
CA2158856A1 (fr) 1994-10-13
DE69411902T2 (de) 1999-04-08
EP0693139A1 (fr) 1996-01-24
JP2968147B2 (ja) 1999-10-25
CN1093415A (zh) 1994-10-12
TW301675B (fr) 1997-04-01
DE69411902D1 (de) 1998-08-27
EP0693139B1 (fr) 1998-07-22

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