US20090242081A1 - Aluminum Treatment Composition - Google Patents

Aluminum Treatment Composition Download PDF

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Publication number
US20090242081A1
US20090242081A1 US12/055,539 US5553908A US2009242081A1 US 20090242081 A1 US20090242081 A1 US 20090242081A1 US 5553908 A US5553908 A US 5553908A US 2009242081 A1 US2009242081 A1 US 2009242081A1
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United States
Prior art keywords
source
ions
group
conversion coating
ammonium
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.)
Abandoned
Application number
US12/055,539
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English (en)
Inventor
Richard Bauer
Michael Malik
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.)
MacDermid Inc
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Individual
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 Individual filed Critical Individual
Priority to US12/055,539 priority Critical patent/US20090242081A1/en
Assigned to MACDERMID, INCORPORATED reassignment MACDERMID, INCORPORATED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BAUER, RICHARD, MALIK, MICHAEL
Priority to EP09725820.6A priority patent/EP2265740A4/fr
Priority to PCT/US2009/034457 priority patent/WO2009120431A1/fr
Priority to CN200980109254.4A priority patent/CN102144042B/zh
Priority to JP2011501862A priority patent/JP5214019B2/ja
Priority to TW098107298A priority patent/TWI388693B/zh
Publication of US20090242081A1 publication Critical patent/US20090242081A1/en
Abandoned 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/10—Anti-corrosive paints containing metal dust
    • C09D5/103—Anti-corrosive paints containing metal dust containing Al
    • 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
    • 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
    • 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 present invention relates generally to compositions and methods for the formation of protective, corrosion-inhibiting coatings on metals, or other materials coated with metals.
  • Non-alloyed specimens of these metals typically form a natural oxide film that will protect them somewhat and reduce their overall rate of corrosion.
  • alloys of these metals are particularly sensitive to corrosive attack.
  • these materials can also have a significant problem with paint adhesion, because the as-formed metal surfaces are typically very smooth, and tend to form weakly bound surface oxides, which do not normally provide a robust base on which subsequent applied paints can anchor themselves.
  • One method of enhancing the corrosion resistance of metal alloys is through the use of a conversion coating, which is a self-healing, corrosion-inhibiting layer formed during intentional exposure of the metal or metal alloy to a chemically reactive solution.
  • Conversion coatings are particularly useful in surface treatment of metals such as steel, zinc, aluminum and magnesium.
  • the conversion coating process forms an adherent surface containing an integral corrosion inhibitor that can provide protection to coating breaches.
  • the metal is exposed to a compound that chemically alters the surface and forms a coating that provides a high degree of corrosion resistance.
  • a chemical conversion coating applied to the surface of a less-noble alloy can reduce the extent and severity of aqueous corrosion, provide long-term property stability, and extend the useful life of the object of manufacture.
  • a critical feature of effective conversion coatings is their ability to provide corrosion protection to the base metal in the presence of a coating breach.
  • Conversion coatings grow an oxide coating on the metal without an externally applied electrical potential.
  • the protective film is produced by a chemical redox reaction between the metal surface and the conversion coating solution.
  • the film is composed both of an oxide and integral corrosion inhibitor species formed during exposure to the conversion coating solution.
  • the conversion-coated surface may be left bare or afforded further protection by the application of additional films or coatings.
  • Conversion coatings need to adhere to the substrate and should also result in a surface that will promote the formation of a strong bond with subsequently applied coatings. Bonding with subsequently applied coatings is a function of the morphology and chemical composition of the conversion coating. Adhesion promoting surface treatments may exhibit corrosion inhibiting characteristics.
  • a conversion coating, as described herein, may also be considered to be an “adhesion promoter” and vice versa.
  • Conversion coatings are usually formed by the application of a conversion coating solution to the metal surface.
  • the solution can be applied by immersion, spray, fogging, wiping, or other similar means depending on the complexity of the surface of the substrate being treated.
  • the present invention relates generally to an aqueous conversion coating composition
  • an aqueous conversion coating composition comprising:
  • the present invention also relates to a method of using the aqueous conversion coating composition of the invention to treat metal substrates such as aluminum and aluminum alloy substrates to provide an improved conversion coating thereon.
  • the aqueous conversion coating composition of the invention is substantially free of phosphorous and/or chromium.
  • the present invention relates generally to acidic aqueous conversion coatings for the pretreatment of metals, such as aluminum and aluminum alloys, zinc, zinc alloys, magnesium and magnesium alloys and steel, and to a process for improving the corrosion resistant properties of such metal substrates.
  • metals such as aluminum and aluminum alloys, zinc, zinc alloys, magnesium and magnesium alloys and steel
  • the present invention relates generally to compositions for pretreating aluminum and aluminum alloy substrates and to a process of pretreating aluminum and aluminum alloy substrates at temperatures ranging from ambient temperatures up to about 200° F.
  • These pretreatment compositions typically comprise an acidic aqueous solution having a pH in the range of about 0.5 to about 6 and preferably from about 3 to 5.
  • the pretreatment composition of the invention is an aqueous solution that typically comprises:
  • the source of aluminum ions is ammonium hexafluoride aluminate.
  • ammonium hexafluoride aluminate is typically preferred, alkali hexafluoride aluminates such as sodium hexafluoride aluminate may also be used in the practice of the present invention.
  • the source of aluminum ions is pure aluminum powder which is used in combination with hexafluorotitanic acid, whereby the aluminum powder is thus dissolved in the solution by the acidity of the hexafluorotitanic acid.
  • Fluoro compounds usable in the practice of the invention include for example ammonium hexafluoride aluminate and hexafluorotitanic acid. Other similar fluoro compounds may also used.
  • the potassium, lithium, sodium, and ammonium salts of hexafluorotitanic acid works especially well for this application, with ammonium performing the best.
  • fluoroaluminates e.g., AlF 6 ⁇ 3 or AlF 4 ⁇ 1
  • fluoroborates e.g., BF 4 ⁇ 1
  • fluorogallates e.g., GaF 4 ⁇ 1
  • fluoroindates e.g., InF 4 ⁇ 1
  • fluorogermanates e.g., GeF 6 ⁇ 2
  • fluorostannates e.g., SnF 6 ⁇ 2
  • fluorophosphates e.g., PF 6 ⁇ 1
  • fluoroarsenates e.g., AsF 6 ⁇ 1
  • fluoroantimonates e.g., SbF 6 ⁇ 1
  • fluorobismuthates e.g., BiF 6 ⁇ 1
  • fluorosulfates e.g., SF 6 ⁇ 2
  • fluoroselenates e.g., SeF
  • Water-soluble potassium, sodium, lithium, or ammonium salts of these anions are typical, with ammonium salts of these anions being preferred.
  • One particularly preferred compound for use in compositions of the invention is ammonium hexafluoride aluminate.
  • the pH adjuster which may include one or more organic acids, inorganic acids, complex fluorides, alkali metal salts, ammonia or a salt thereof, can be added to adjust the pH.
  • these additives include, without limitation, acetic acid, benzoic acid, citric acid, lactic acid, malic acid, propionic acid, succinic acid, tartaric acid, adipic acid, 1,2,3,4-butanetetracarboxylic acid, fluoboric acid, sulfurric acid, sulfonic acid, methane sulfonic acid, methane disulfonic acid, nitric acid, silicic acid, hydrosilicofluoric acid, hydrofluoric acid, phosphoric acid, fluorozirconic acid, fluorotitanic acid, sodium hydroxide, ammonia, ammonium bicarbonate, ammonium carbonate, sodium carbonate, and sodium bicarbonate and combinations of one or more of the foregoing.
  • Other compounds would also be known to those skilled in
  • composition of the invention also includes at least one Group VIB metal compound which is selected from the group consisting of tungstate compounds and trivalent chromium compounds.
  • the Group VIB metal compound is chromium, in particular trivalent chromium, which may be added to the solution as any water-soluble trivalent chromium compound, preferably as a trivalent chromium salt.
  • a preferred trivalent chromium compound usable in the compositions of the invention comprises basic chromium(III)sulfate (chrometan), which has the formula CrOHSO 4 .Na 2 SO 4 xH 2 O and contains about 17.2 percent of chromium.
  • Other trivalent chromium compounds that may be usable in the practice of the invention include for example chromium(III)thiocyanate complexes as described in U.S. Pat. No.
  • chromium (III) formate chromium (III) acetate, chromium (III) bromide hexahydrate, chromium (III) chloride hexahydrate, chromium (III) iodate, hydrate, chromium (III) nitrate, chromium (III) oxalate, chromium (III) orthophosphate, chromium (III) sulfate, hexamine chromium (III) chloride, hexaurea chromium (III) fluosilicate, chromium (III) fluoride tetrahydrate, chromium (III) iodide nonahydride, chromium (III) nitrate hexammonate, chromium (III) potassium oxalate, various art known equivalents thereof, and combinations of one or more of the foregoing.
  • the Group VIB metal is tungsten.
  • the tungsten is typically added to the composition as a source of tungstate ions.
  • the source of tungstate ions includes all tungstates but most specifically all ortho-tungstates, meta-tungstates and para-tungstates, polytungstates, hetero-polytungstates, isopolytungstates, peroxytungstates, and combinations thereof.
  • a source of meta- or para-tungstate is preferred.
  • Suitable sources of tungstate ions include sodium, potassium, lithium, calcium, cerium, barium, magnesium, strontium, hydrogen and ammonium tungstate salts, such as ammonium metatungstate, potassium metatungstate, sodium metatungstate, tungstic acid, sodium tungstate, potassium tungstate and ammonium tungstate.
  • a preservative is hexahydro-1,3,5-tris(2-hydroxyethyl)-s-triazine, sold under the tradename Surcide P (available from Surety Laboratories, Cranford, N.J.). Other similar preservatives would also be known to those skilled in the art.
  • a first formulation (Formula A) that has been determined to provide improved corrosion protection of metal substrates, such as aluminum, aluminum alloys, zinc, zinc alloys, magnesium, magnesium alloys and steel prepared in accordance with the present invention comprises:
  • Table 1 sets forth one preferred composition for Formula A prepared in accordance with the present invention.
  • Table 2 sets forth examples various alternate use concentrations for the Formula A solution prepared in accordance with the present invention.
  • Form B Another formulation (Formula B) that has been determined to provide improved corrosion protection of metal substrates, including aluminum, aluminum alloys, zinc, zinc alloys, magnesium, magnesium alloys and steel prepared in accordance with the present invention comprises:
  • Table 3 sets forth one preferred composition for Formula B prepared in accordance with the present invention.
  • Table 4 sets forth examples of various alternate use concentrations for the Formula B solution prepared in accordance with the present invention.
  • the metal substrate for use in the process of the present invention may be any substrate at least having a metal surface.
  • usable substrates include those having a surface made of iron, aluminum, magnesium, zinc, copper, tin or an alloy containing any of these metals. Particularly preferred are steel sheet substrates and aluminum or aluminum alloy substrates.
  • steel sheet substrates examples include hot-dip galvanized steel sheets, electrogalvanized steel sheets, iron-zinc alloy plated steel sheets, nickel-zinc alloy plated steel sheets, aluminum-zinc alloy plated steel sheets and the like. Also usable as steel sheet substrates are zinc-based metal plated steel sheets that have been subjected to chemical conversion treatment such as chromate treatment, zinc phosphate treatment or composite oxide film treatment. Further, a steel sheet assembly can be employed as a steel sheet substrate.
  • the coating composition of the present invention can be applied to a metal substrate by any known process, such as dip coating, shower coating, spray coating, roll coating and electrocoating.
  • the duration of contact ranges from about 30 seconds to about 5 minutes, but longer contact may be required if the solution is weak or if the temperature of the solution is relatively low.
  • the aqueous solution temperature is normally below 100° C., for example in the range of 15° to 75° C., and more preferably at about ambient temperature (e.g. about 25° C.).
  • the composition be dried for about 2 seconds to about 30 minutes by heating under such conditions that the substrate reaches a maximum temperature of about 60 to 250° C.
  • the substrates Prior to performing the trivalent chromium pretreatment, the substrates may be treated by cleaning and/or activating as is generally well known in the art. The substrates may then be contacted with the composition of the invention for a sufficient period of time to form a conversion coating layer on the surface of the substrate and then allowed to dry.
  • compositions of the present invention can also be used to improve the adhesion and corrosion resistant properties of metal coated substrates, as suggested for example in U.S. Pat. Nos. 6,511,532, 6,527,841, and 6,663,700 to Matzdorf et al., the subject matter of each of which is herein incorporated by reference in its entirety.
  • post-treatment coatings are typically contacted with the metal being treated after formation of the initial coating and therefore the post-treatments normally have no direct contact with the underlying substrate, except possibly through some pores in the metal coating.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)
US12/055,539 2008-03-26 2008-03-26 Aluminum Treatment Composition Abandoned US20090242081A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US12/055,539 US20090242081A1 (en) 2008-03-26 2008-03-26 Aluminum Treatment Composition
EP09725820.6A EP2265740A4 (fr) 2008-03-26 2009-02-19 Composition de traitement d'aluminium
PCT/US2009/034457 WO2009120431A1 (fr) 2008-03-26 2009-02-19 Composition de traitement d'aluminium
CN200980109254.4A CN102144042B (zh) 2008-03-26 2009-02-19 铝处理组合物
JP2011501862A JP5214019B2 (ja) 2008-03-26 2009-02-19 アルミニウム処理組成物
TW098107298A TWI388693B (zh) 2008-03-26 2009-03-06 鋁處理組成物

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US12/055,539 US20090242081A1 (en) 2008-03-26 2008-03-26 Aluminum Treatment Composition

Publications (1)

Publication Number Publication Date
US20090242081A1 true US20090242081A1 (en) 2009-10-01

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Family Applications (1)

Application Number Title Priority Date Filing Date
US12/055,539 Abandoned US20090242081A1 (en) 2008-03-26 2008-03-26 Aluminum Treatment Composition

Country Status (6)

Country Link
US (1) US20090242081A1 (fr)
EP (1) EP2265740A4 (fr)
JP (1) JP5214019B2 (fr)
CN (1) CN102144042B (fr)
TW (1) TWI388693B (fr)
WO (1) WO2009120431A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102965654A (zh) * 2012-12-16 2013-03-13 况金权 一种高耐盐雾的铝材钝化剂及其制备方法
US20140041764A1 (en) * 2012-08-07 2014-02-13 Roberto Zoboli Steel Pre-Paint Treatment Composition
CN104894547A (zh) * 2015-06-12 2015-09-09 新乡学院 应用于6061铝合金表面的氟钛酸盐转化液以及使用方法
CN111394718A (zh) * 2020-03-04 2020-07-10 博罗县东明化工有限公司 钝化液及铜表面成膜处理方法
CN116240535A (zh) * 2022-12-13 2023-06-09 广东东明新材科技有限公司 镁合金钛铝钨皮膜处理剂、制备方法以及镁合金表面处理方法

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CN104099602B (zh) * 2014-06-19 2016-08-17 锐展(铜陵)科技有限公司 一种溴酸盐铝合金表面处理剂
CN104099597B (zh) * 2014-06-19 2016-07-06 锐展(铜陵)科技有限公司 一种火山灰铝合金表面处理剂
CN109576695A (zh) * 2019-01-17 2019-04-05 温岭德利众机械制造有限公司 一种铝件用钝化剂和铝件表面处理的方法
CN112323055B (zh) * 2020-11-06 2022-11-18 上海理工大学 用于制备镁合金化学转化膜的锑酸盐溶液体系及使用方法
CN115161627B (zh) * 2022-06-13 2024-04-23 东莞理工学院 一种镁合金表面转化液及镁合金表面转化膜的制备方法

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