WO2009138022A1 - Composition pour revêtement de conversion d'un substrat métallique zincifère, procédé pour traiter un substrat métallique zincifère, substrat métallique zincifère traité et son utilisation - Google Patents

Composition pour revêtement de conversion d'un substrat métallique zincifère, procédé pour traiter un substrat métallique zincifère, substrat métallique zincifère traité et son utilisation Download PDF

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Publication number
WO2009138022A1
WO2009138022A1 PCT/CN2009/071731 CN2009071731W WO2009138022A1 WO 2009138022 A1 WO2009138022 A1 WO 2009138022A1 CN 2009071731 W CN2009071731 W CN 2009071731W WO 2009138022 A1 WO2009138022 A1 WO 2009138022A1
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composition
metal substrate
zinc
vanadium
vanadium ion
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PCT/CN2009/071731
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English (en)
Chinese (zh)
Inventor
触-庵派西提才
洪静娴
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汉高两合股份公司
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Publication of WO2009138022A1 publication Critical patent/WO2009138022A1/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
    • 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
    • C23C22/36—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 containing also phosphates
    • C23C22/361—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 containing also phosphates containing titanium, zirconium or hafnium compounds
    • 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
    • C23C22/40—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 molybdates, tungstates or vanadates
    • C23C22/44—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 molybdates, tungstates or vanadates containing also fluorides or complex fluorides

Definitions

  • the present invention relates to a composition for conversion coating of a zinc-containing metal substrate which is aqueous chromium-free and which contains a source of vanadium ions and a phosphate ion and a fluorotitanium complex having a molar ratio to vanadium ions.
  • the present invention also includes a method of treating a zinc-containing metal substrate with the composition, which composition is particularly suitable for coating-type coating processes in the coil coating industry.
  • the invention also encompasses zinc-containing metal substrates treated by this method and the use of the zinc-containing metal substrates in the production of large household appliances, household appliances, vehicles, and in the construction industry. Background technique
  • Short-term corrosion protection of steel strips containing zinc, especially galvanized or galvanized alloys, is usually based on protective oil or, if necessary, conversion treatments such as phosphating or passivation.
  • conversion treatment refers to the treatment of a metal surface with an aqueous solution, during which the original metal surface layer is converted into an inorganic layer comprising the cations and anions in the treated aqueous solution and the treated base metal. cation.
  • the range of metal conversion treatments includes providing the metal with a corrosion protection layer and providing a tie layer to enhance adhesion between the metal surface and the organic coating applied thereafter.
  • the adhesion protection and the adhesion to the subsequently applied organic coating are achieved by a chromate conversion treatment.
  • the formation of an effective barrier layer by phosphating has been a well established method.
  • the process itself is a complex multi-step process that requires control of a large number of bath parameters while at the same time providing less decorative coatings relative to chromate passivation. Since these chromate coatings contain dangerous hexavalent chromium, the surface treatment industry is looking for a way to replace chromate conversion to comply with recent national and local laws and regulations in force in the European Union.
  • U.S. Patent 6,692,583 discloses an aqueous chromium-free conversion coated composition for a magnesium substrate comprising only a) a vanadate ion source, b) a phosphate ion source and c) a nitrate ion source.
  • a further optional ingredient that can be used as the coating composition can include a source of borate ions, fluoride ions and/or fluoroborate ions.
  • U.S. Patent No. 2007/0068602 discloses a preparation method and a composition coated on a surface of an iron metal with a conversion coating containing zirconium or vanadium, which is substantially free of components and tannic acid forming an organic film.
  • the most important aspect is to determine the ratio of vanadium to phosphate ions of from 0.5 to 2.4, and to minimize the amount of phosphate for environmental reasons.
  • Another important aspect is that the ratio of zirconium atoms to vanadium atoms is in the range of 1:2-2:1. Summary of the invention
  • the technical problem to be solved by the present invention is to overcome the existing conversion site for a zinc-containing metal substrate.
  • a complex, chrome-contaminated defect is provided to provide a stable aqueous chromium-free conversion coating composition containing a vanadium ion source that provides a thin inorganic protective layer to the zinc-containing metal surface.
  • the thin inorganic layer formed on the zinc-containing metal substrate provides short-term protection against corrosion, especially against the formation of white rust before the application of the next protective coating such as an organic primer and/or paint.
  • the thin inorganic layer formed during the application of the composition of the present invention also requires excellent paint adhesion.
  • such aqueous chromium-free compositions for conversion coating are also suitable for coating coating processes which are very popular in the coil coating industry.
  • the term “stable” means that the composition remains clear without precipitation at temperatures up to 60 ° C and maintained for at least 24 hours.
  • chromium-free means that the total amount of chromium in the composition is less than 1 ppm, preferably less than 0.1 ppm. A small amount of chromium below this total amount may accumulate in the composition because, in the treatment of the zinc-containing substrate, the zinc-containing substrate may be compounded with a small amount of chromium as an alloy component or as an inorganic component of the pretreated metal substrate.
  • zinc-containing metal substrates include zinc substrates, hot-dip galvanized steel substrates, electrolytic zinc steel substrates, Galfan®, Galvalume®, and Galvannealed®.
  • the "vanadium ion" as used in the present invention means a vanadium element which exists in an ionic state, and its ionic state may be a charged vanadium atom such as v 5+ or a charged vanadium atom-containing atomic group such as vo 3 - ,
  • Chromium-free solution containing components: (a) phosphoric acid, (b) fluorotitanium complex and (c) vanadium ion source; the content of each component is: vanadium ion provided by vanadium ion source (c)
  • the concentration in the composition is lg/L ⁇ 20 g/L, and the molar ratio of the vanadium ion (c) to the phosphate ion (a) supplied by the phosphoric acid in the composition is 1:4 to 1:2,
  • the molar ratio of the vanadium ion (c) to the fluorotitanium complex (b) in the composition is 3:2 to 3:1.
  • the molar ratio of vanadium ion to phosphate ion exceeds the specified 1:2, the aqueous chromium-free converted coating composition becomes unstable and precipitation occurs.
  • the above ratio of less than 1:4 causes the composition to become turbid, and treatment of the zinc-containing substrate with the composition results in poor corrosion test results.
  • the molar ratio of vanadium ion to phosphate ion in the composition is preferably 1:3.
  • the ratio of the vanadium ion to the fluorotitanium complex in the aqueous chromium-free conversion coating composition of the present invention is greater than the specified 3:1, the inorganic layer obtained by treating the zinc-containing metal substrate with the composition is resistant to corrosion. Poor performance.
  • the ratio of vanadium ion to fluorotitanium complex in the composition is preferably 2:1.
  • the aqueous chromium-free conversion coated composition of the present invention further comprises one or more components (d) selected from the group consisting of boron and/or silicon fluorine composites, such as sodium tetrafluoroborate , ammonium fluoroborate, hexafluorosilicic acid and sodium hexafluorosilicate are beneficial to the formation of inorganic layers.
  • boron and/or silicon fluorine composites such as sodium tetrafluoroborate , ammonium fluoroborate, hexafluorosilicic acid and sodium hexafluorosilicate are beneficial to the formation of inorganic layers.
  • silicon fluorine composites such as sodium tetrafluoroborate , ammonium fluoroborate, hexafluorosilicic acid and sodium hexafluorosilicate are beneficial to the formation of inorganic layers.
  • the most important metal and metalloid elements are vanadium elements and titanium elements. Therefore, the molar ratio of the vanadium ion to the fluorine complex of boron and/or silicon is preferably 1, more preferably 2. In the aqueous chromium-free conversion coated composition, a relatively large content of the fluorine composite of boron and/or silicon is disadvantageous for passivating the formation of the inorganic conversion layer.
  • the molar ratio of vanadium ions to boron and/or silicon fluoride complex in the composition is greater than 4: 1, the corrosion protection and the adhesion to paint are not visible.
  • a preferred vanadium ion source is a vanadate having a vanadium atom oxidation number greater than + valence. These vanadates are added to the aqueous composition as an alkaline solution to form the conversion coated composition of the present invention.
  • a preferred source of vanadium ions may also be a compound such as vanadium (IV) oxide, vanadium pentoxide (V), sodium metavanadate (V) and ammonium metavanadate (V).
  • the most preferred vanadium of the invention is +V
  • a wet film formed of 14 g/L so as to be coated on a metal surface, for example, with a squeeze bar, can form a thin inorganic layer after drying.
  • a vanadium ion is preferably used in an amount of more than 6 g/L, more preferably more than 10 g/L, and a composition obtained by coating a wet film formed on a metal surface to form a uniform inorganic conversion layer.
  • the aqueous conversion-coated composition of the present invention is an acidic solution.
  • the pH value is preferably
  • the content of the organic polymer in these compositions of the present invention is extremely small, not more than 1 ppm.
  • the organic polymer is silicon germanium, a resin or a wax as commonly found in the art.
  • Higher levels of organic polymer form an inorganic-organic hybrid coating that is less heat and smothering than a fully inorganic coated coating.
  • the zinc-containing substrate can withstand a peak metal temperature of 400 ° C for at least 5 minutes without any change in surface color and corrosion resistance and paint adhesion.
  • compositions of the present invention do not contain any source of nitrate ions or nitrite ions in excess of greater than 1 ppm, preferably completely free of any source of nitrate ions or sources of nitrite ions.
  • the composition may release dangerous nitrogen-containing gases.
  • the preparation method of the composition of the present invention is a conventional method of mixing the components in the art, and may also be obtained by diluting the formulation composition described below with water.
  • the present invention also relates to a formulated composition which, by diluting the formulated composition with water, produces the above aqueous chromium-free composition for conversion coating of a zinc-containing metal substrate, which is an aqueous chromium-free solution comprising the following components: a) phosphoric acid, (b) fluorotitanium complex and (c) vanadium ion source; wherein the vanadium ion source provides a vanadium ion concentration of not more than 85 g/L, but not less than 20 g/L, the formulation composition is to satisfy: i) a molar ratio of vanadium ions to phosphate ions provided by phosphoric acid 1: 4, preferably
  • the vanadium ion content of the formulated composition cannot be higher. Because of the limited solubility of the ingredients in water for the formulation, the concentration of vanadium is about 85 g/L. Therefore, according to the present invention, when the concentration of each aqueous component is higher, the composition becomes unstable, and precipitation of components occurs.
  • the formulation composition can also be applied directly to a zinc-containing substrate.
  • the formulated composition is preferably diluted with water to have a ratio of 10 to water, more preferably 4.
  • the composition of the vanadium having a concentration of 20 g/L can be directly applied to the zinc-containing substrate, or it can be diluted with water and then coated.
  • the specific method can be determined according to the actual needs of the site. The same is true for other concentrations of this configuration of the composition.
  • the method of preparing the formulated composition is also a conventional method of mixing the components in the art.
  • the present invention primarily provides a composition which is an aqueous chromium-free solution comprising components: (a) phosphoric acid, (b) a fluorotitanium complex, and (c) a source of vanadium ions; wherein, provided by a source of vanadium ions
  • the concentration of vanadium ion (c) in the composition is lg / L ⁇ 85g / L
  • the molar ratio of vanadium ion (c) to phosphate ion (a) provided by phosphoric acid in the composition is 1: 4 ⁇ 1: 2
  • the composition can be directly used for conversion coating zinc-containing metal substrate,
  • the composition having a vanadium ion concentration of lg/L to 20 g/L is directly used for transforming and coating a zinc-containing metal substrate, and the composition having a vanadium ion concentration of 20 g/L to 85 g/L can be used according to the composition.
  • the present invention also discloses a method of forming a conversion coating on a zinc-containing metal substrate wherein the zinc-containing metal substrate is simply contacted with the aqueous chromium-free conversion coated composition of the present invention.
  • the treatment solution in the process i.e., the aqueous chromium-free conversion coated composition of the present invention
  • the treatment solution in the process can be based on conventional industrial coating techniques such as soaking, spraying, wiping, and rubber rolling and/or roller press applications. It is applied to the metal surface.
  • the wet film of the aqueous chromium-free conversion coated composition adhered to the metal substrate must be dried immediately after the zinc-containing metal surface is contacted with the treatment solution.
  • the drying method is preferably not It is required to complete any of the aforementioned intermediate cleaning steps.
  • Such coating methods are known in technical terms as coating-type coating methods and/or no-clean coating methods. After the volatile components in the treatment solution adhered to the metal surface are evaporated, a conversion coating is formed.
  • the coating type coating method preferably has a peak metal temperature of at least 60 ° C, more preferably 80 ° C, but preferably does not exceed 120 ° C. At lower peak metal temperatures, the drying process is time consuming and technically inefficient. Conversely, at higher peak metal temperatures, an increase in the rate of evaporation of water impedes the formation of the conversion layer, so that only a less inorganic layer can be precipitated and the entire zinc-containing substrate surface cannot be chemically converted.
  • the invention also includes transforming the coated zinc-containing metal substrate itself according to the method of the invention, wherein the dried film (i.e., dry film) of the conversion coating has a mass of at least 0.15 g/m 2 , preferably at least 0.3 g/m. 2 , but not more than 2 g / m 2 , preferably not more than 1 g / m 2 , the best can not be greater than 0.6 g / m
  • the weight of the dried film of the conversion layer derived from the thin wet film formed by coating the pure inorganic aqueous coating composition of the present invention on a zinc-containing metal substrate is limited. Because the mechanical stability of the pure inorganic coating decreases as the film thickness increases. Therefore, in a preferred embodiment, the concentration of the organic polymer in the coating composition of the present invention cannot be greater than 1 ppm, and the weight of the dried film does not exceed 1 g/m.
  • the zinc-containing metal substrate treated in accordance with the present invention can be used to coat a multilayer coating thereon in the field of industrial metal surface treatment.
  • the multilayer coating comprises at least one layer of an organic coating as the final topcoat or paint, or as a primer coating.
  • these coatings are existing coatings in the metal surface treatment industry.
  • the use of the converted coated zinc-containing metal substrate of the present invention is primarily, but not limited to, the production of large household appliances, household appliances, vehicles, and in the construction industry. It is a matter of course that the present invention also includes corrosion resistance and paint adhesion which are essential prerequisites and other similar uses of the zinc-containing substrate imparted by the inorganic conversion coated compositions of the present invention.
  • the beneficial effects of the present invention are as follows compared to the prior art: Organic polymerization in the composition of the present invention
  • the content of the compound is extremely small, not more than 1 ppm, so that the coating has excellent heat resistance and enthalpy; and is completely free of any source of nitrate ions or nitrite ions which may release dangerous nitrogen-containing gas;
  • After the surface conversion treatment of the zinc-containing material no additional cleaning is required, in particular, chromate passivation cleaning is not required, so that the conversion treatment is simple and does not cause chromium pollution to the environment.
  • compositions VIII, B, C, D, H, I, J and K of the present invention were formulated in accordance with Tables 1, 3, and 4, and then dissolved in water.
  • the component vanadium pentoxide was added to the required amount with an alkali solution containing 3.17 wt% V 2 O 5 , 3.65 wt% NaOH.
  • the component vanadium dioxide was added to the desired amount with an alkali solution containing 3.17 wt% V0 2 , 5.32 wt% NaOH.
  • the other components are simple blends.
  • the molar ratios of the particular elements in each composition are shown in Tables 2 and 5.
  • Formulation compositions L and M were diluted 10-fold and 4-fold, respectively, with water to obtain a stable composition for transforming and coating a zinc-containing metal substrate of the present invention.
  • Formulation Composition N can be used directly for conversion coating of zinc-containing metal substrates without dilution.
  • the compositions of the present invention, B, C, D, H, I, J and K and the formulated compositions L, M and N are all stable aqueous solutions in which the total chromium content is less than 0.1 ppm and is completely free of organic A source of polymer, nitrate or nitrite ion.
  • compositions VIII, B, C and D of the invention With ⁇ 1/ wt%
  • compositions of the present invention 11, J, K, and component compositions of the formulated compositions L, M, N, i wt%
  • Example 2 Method for containing zinc metal substrate and conversion coating
  • a zinc-containing steel substrate (HDG, hot dip galvanized steel sheet; EG, electrolytically galvanized steel sheet; GL, Galvalume®) was separately contacted with the composition A-D of the present invention (see Table 6). After the contact, the wet film of the composition adhered to the surface of the zinc-containing metal substrate was immediately dried without an intermediate cleaning step.
  • the peak metal temperature used for drying is as follows. Among them, "A-HDG-1" means the first HDG substrate treated with composition A.
  • the dry film quality of the formed zinc-containing metal substrate conversion coating is shown in Table 6.
  • the formulated compositions L and M were diluted 10 and 4 times with water, respectively, and the resulting solution and the preparation composition N were respectively coated with a zinc-containing steel substrate HDG as described above, wherein the peak metal temperature was 80 ° C, and the obtained conversion coating was dry film.
  • the masses were 0.15, 1 and 2 g/m 2 , respectively .
  • composition of the present invention was compared by a neutral salt spray test (NSST) with white rust on various steel substrates (HDG, EG, GL) and untreated steel substrates coated with A-D (see Table 6).
  • NST neutral salt spray test
  • the use of white rust formed on different zinc-containing substrates in neutral salt spray tests as an indicator of short-term corrosion resistance is reported in the literature (according to ASTM B117-03).
  • Galvalume treats these steel sheets with compositions of similar type to the present invention, but the amount of phosphate ions or fluorotitanium complexes in the composition exceeds the range of molar ratios specified herein.
  • These compositions of a type similar to the compositions of the invention are E, F, G.
  • the compositions other than those shown in Table 7 of these non-inventive compositions are the same as Composition C of the present invention.
  • Table 8 shows these treated galvanized steel sheets The result of white rust formation in a neutral salt spray test.

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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)

Abstract

L'invention porte sur une composition pour un revêtement de conversion d'un substrat métallique zincifère, laquelle composition est une solution aqueuse sans chrome et comprend les composants suivants : (a) de l'acide phosphorique, (b) du fluorure de titane complexe, (c) une source d'ions vanadium ; la teneur de chaque composant, respectivement, est la suivante : la concentration d'ions vanadium (c) issus de la source d'ions vanadium dans la composition est comprise entre 1 g/l à 20 g/l, le rapport molaire des ions vanadium (c) aux ions phosphates (a) étant compris entre 1:4 et 1:2, le rapport molaire des ions vanadium (c) au fluorure de titane complexe (b) est compris entre 3:2 et 3:1. L'invention porte également sur une formulation de composition utile pour produire la composition ci-dessus par dilution avec de l'eau, sur un procédé pour mettre en contact le substrat métallique zincifère avec la composition ci-dessus pour former un revêtement de conversion, et sur un substrat métallique zincifère traité par conversion obtenu par le procédé ci-dessus et sur son utilisation. Un nettoyage additionnel n'est pas nécessaire après le traitement par conversion de la surface du substrat métallique zincifère à l'aide de la composition ci-dessus, et, en particulier, un nettoyage de passivation de chromate n'est pas requis ; par conséquent, l'étape de traitement de conversion est facile et ne produit pas de pollution de l'environnement par le chrome.
PCT/CN2009/071731 2008-05-12 2009-05-11 Composition pour revêtement de conversion d'un substrat métallique zincifère, procédé pour traiter un substrat métallique zincifère, substrat métallique zincifère traité et son utilisation WO2009138022A1 (fr)

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CN200810096526.9 2008-05-12
CN2008100965269A CN101580654B (zh) 2008-05-12 2008-05-12 一种用于转化涂布含锌金属基底的组合物及其处理方法和该处理过的含锌金属基底及其用途

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US7964030B1 (en) * 2010-04-12 2011-06-21 Fu Zhun Precision Industry (Shen Zhen) Co., Ltd. Magnesium coating solution and method for preparing the same

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CN108796584B (zh) * 2017-04-28 2020-08-25 宝山钢铁股份有限公司 一种镀锡产品表面钝化膜结构柔性控制方法
US11293104B2 (en) * 2017-06-27 2022-04-05 Bulk Chemicals, Inc. Inorganic non-chrome aqueous treatment composition and process for coating metal surfaces
CN107868548B (zh) * 2017-12-06 2020-03-17 立邦（上海）化工有限公司 用于铝基材料的防腐处理剂及其生产方法

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US6027579A (en) * 1997-07-07 2000-02-22 Coral Chemical Company Non-chrome rinse for phosphate coated ferrous metals
US20060169363A1 (en) * 2005-01-14 2006-08-03 Jasdeep Sohi Stable, non-chrome, thin-film organic passivates
US20070068602A1 (en) * 2005-09-28 2007-03-29 Coral Chemical Company Zirconium-vanadium conversion coating compositions for ferrous metals and a method for providing conversion coatings

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US5772865A (en) * 1995-10-04 1998-06-30 Dipsol Chemicals Co., Ltd. Electrolytic conversion solution for treating metal surface and method for electrolytic conversion
US6027579A (en) * 1997-07-07 2000-02-22 Coral Chemical Company Non-chrome rinse for phosphate coated ferrous metals
US20060169363A1 (en) * 2005-01-14 2006-08-03 Jasdeep Sohi Stable, non-chrome, thin-film organic passivates
US20070068602A1 (en) * 2005-09-28 2007-03-29 Coral Chemical Company Zirconium-vanadium conversion coating compositions for ferrous metals and a method for providing conversion coatings

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7964030B1 (en) * 2010-04-12 2011-06-21 Fu Zhun Precision Industry (Shen Zhen) Co., Ltd. Magnesium coating solution and method for preparing the same

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