WO2007080849A1 - Procede de traitement par conversion chimique de la surface d’un materiau en aluminium et materiau en aluminium - Google Patents

Procede de traitement par conversion chimique de la surface d’un materiau en aluminium et materiau en aluminium Download PDF

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Publication number
WO2007080849A1
WO2007080849A1 PCT/JP2007/050077 JP2007050077W WO2007080849A1 WO 2007080849 A1 WO2007080849 A1 WO 2007080849A1 JP 2007050077 W JP2007050077 W JP 2007050077W WO 2007080849 A1 WO2007080849 A1 WO 2007080849A1
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WIPO (PCT)
Prior art keywords
concentration
chemical conversion
aluminum material
conversion treatment
aluminum
Prior art date
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PCT/JP2007/050077
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English (en)
Japanese (ja)
Inventor
Mitsuo Suzuki
Takeshi Ono
Original Assignee
Mitsui Mining & Smelting Co., Ltd.
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.)
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Publication date
Application filed by Mitsui Mining & Smelting Co., Ltd. filed Critical Mitsui Mining & Smelting Co., Ltd.
Priority to CN2007800011381A priority Critical patent/CN101356300B/zh
Priority to JP2007553897A priority patent/JPWO2007080849A1/ja
Publication of WO2007080849A1 publication Critical patent/WO2007080849A1/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
    • C23C22/40—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
    • 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 is formed by a surface chemical conversion treatment method for an aluminum material made of aluminum or an aluminum alloy (hereinafter collectively referred to as aluminum and aluminum alloy) and such a surface chemical conversion treatment. More specifically, the aluminum material having a surface that is formed by chemical conversion treatment of the surface of the aluminum material using a treatment liquid that does not contain hexavalent chromium but contains trivalent chromium.
  • the present invention relates to a chemical conversion treatment method and an aluminum material having a film formed by such surface chemical conversion treatment.
  • hexavalent chromium such as alkali chromate method, chromate method, phosphate chromate method, zinc phosphate method, non-chromate chemical conversion treatment method (tannic acid Method) and other various non-chromium systems (for example, see Non-Patent Document 1 and Patent Documents 1 to 6).
  • Non-Patent Document 1 Surface Technology Association, “Surface Technology Handbook”, Nikkan Kogyo Shimbun, February 1998, p. 691
  • Patent Document 1 JP-A-7-90614
  • Patent Document 2 Japanese Patent Laid-Open No. 10-237667
  • Patent Document 3 Japanese Patent Laid-Open No. 11 131254
  • Patent Document 4 Japanese Patent Laid-Open No. 2000-34577
  • Patent Document 5 Japanese Patent Laid-Open No. 2002-249886
  • Patent Document 6 Japanese Patent Laid-Open No. 2002-275649
  • Patent Document 7 Japanese Patent Laid-Open No. 2002-332575
  • Patent Document 8 Japanese Unexamined Patent Application Publication No. 2002-332581
  • Patent Document 9 Japanese Patent Laid-Open No. 2003-213446
  • Patent Document 10 Japanese Patent Application Laid-Open No. 2005-281852
  • the surface of an aluminum material is treated using a treatment liquid containing trivalent chromium, but the chromate method containing hexavalent chromium is treated with the phosphate chromate method. It is an object of the present invention to provide a chemical conversion treatment method for the surface of an aluminum material that can achieve an effect equal to or higher than that, and an aluminum material having a film formed by such a surface chemical conversion treatment.
  • the present inventor has made the surface of the aluminum material anodized and then sealed the surface of the aluminum material with chromium nitrate and vanadine.
  • Aluminum with excellent corrosion resistance and coating adhesion by using a treatment solution containing acid ammonium, potassium titanium fluoride, lithium fluoride and nitric acid at specific temperatures for a specific time.
  • the present invention was completed by finding that a lumber product can be obtained.
  • the surface of the aluminum material has a chromium nitrate concentration of 3 to 12 gZL as Cr (NO),
  • the concentration of ammonium vanadate is 0.5-7 gZL as NH VO,
  • Titanium potassium fluoride concentration is 0.5-3gZL as K TiF
  • Lithium fluoride concentration is 0.5-3gZL as LiF
  • Nitric acid concentration is 0.5 ⁇ 1.8mLZL as HNO
  • Liquid temperature is 40-50 ° C
  • a film is formed by performing chemical conversion treatment for 1 to 5 minutes with a treatment solution.
  • the surface of the aluminum material is subjected to a positive electrode oxidation treatment and then a sealing treatment,
  • Chromium nitrate concentration is 3-12gZL as Cr (NO),
  • the concentration of ammonium vanadate is 0.5-7 gZL as NH VO,
  • Titanium potassium fluoride concentration is 0.5-3gZL as K TiF
  • Lithium fluoride concentration is 0.5-3gZL as LiF
  • Nitric acid concentration is 0.5 ⁇ 1.8mLZL as HNO
  • Liquid temperature is 40-50 ° C
  • a film is formed by performing chemical conversion treatment for 1 to 5 minutes with a treatment solution.
  • the aluminum material of the present invention the surface of the aluminum material,
  • Chromium nitrate concentration is 3-12gZL as Cr (NO),
  • Ammonium vanadate concentration is 0.5-7gZL as NH VO
  • Titanium potassium fluoride concentration is 0.5-3gZL as K TiF
  • Lithium fluoride concentration is 0.5-3gZL as LiF
  • Nitric acid concentration is 0.5 ⁇ 1.8mLZL as HNO
  • Liquid temperature is 40-50 ° C
  • It is characterized by having a film formed by performing chemical conversion treatment for 1 to 5 minutes with the treatment liquid.
  • the surface of the aluminum material is anodized, then sealed,
  • Chromium nitrate concentration is 3-12gZL as Cr (NO),
  • the concentration of ammonium vanadate is 0.5-7 gZL as NH VO,
  • Titanium potassium fluoride concentration is 0.5-3gZL as K TiF
  • Lithium fluoride concentration is 0.5-3gZL as LiF
  • Nitric acid concentration is 0.5 ⁇ 1.8mLZL as HNO, Liquid temperature is 40-50 ° C
  • It is characterized by having a film formed by performing chemical conversion treatment for 1 to 5 minutes with the treatment liquid.
  • the surface of the aluminum material is subjected to chemical conversion treatment using a treatment liquid containing trivalent chromium without containing hexavalent chromium.
  • the chromate method containing hexavalent chromium can achieve the same or higher effect as compared with the case where the phosphoric acid chromate method is used.
  • FIG. 1 is a photograph showing a state after a corrosion resistance test of a test piece subjected to chemical conversion treatment in Example 1.
  • FIG. 2 is a photograph showing a state after a corrosion resistance test of a test piece subjected to chemical conversion treatment in Example 2.
  • FIG. 3 is a photograph showing a state after a corrosion resistance test of a test piece subjected to chemical conversion treatment of Comparative Example 1.
  • FIG. 4 is a photograph showing a state after a corrosion resistance test of a test piece subjected to chemical conversion treatment of Comparative Example 2.
  • FIG. 5 is a photograph showing a state after a corrosion resistance test of a test piece subjected to chemical conversion treatment in Comparative Example 3.
  • FIG. 6 is a photograph showing a state after a corrosion resistance test of a test piece subjected to chemical conversion treatment in Comparative Example 4.
  • FIG. 7 is a photograph showing a state after a corrosion resistance test of a test piece subjected to chemical conversion treatment of Comparative Example 5.
  • FIG. 8 is a photograph showing a state after a corrosion resistance test of a test piece subjected to chemical conversion treatment in Comparative Example 6.
  • FIG. 9 is a photograph showing a state after a corrosion resistance test of a test piece subjected to chemical conversion treatment of Comparative Example 7.
  • the aluminum material subjected to the chemical conversion treatment by the surface chemical conversion treatment method of the present invention all aluminum and aluminum alloys that are practically used in various technical fields, for example, AC1A, AC1B defined in JIS H 5 202, AC2A, AC2B, AC3A, AC4A, AAC4B, AC4C, AC4CH, AC4D, AC5A AC7A AC8A AC8B, AC8C, AC9A, AC9B, etc.
  • Aluminum alloy wrought materials such as 7075 and 8021 are included.
  • the form of the aluminum material product subjected to surface chemical conversion treatment in the present invention examples thereof include a mold forging product, a sand mold forging product, a die casting, a wrought material, and the like.
  • the surface of the aluminum material is preferably pretreated.
  • the pretreatment can be performed by any of a mechanical method, a solvent method, an alkali method, and a pickling method, for example.
  • it can be carried out by immersing in an aqueous solution of Actan 70 (Meltex, ammonium acid fluoride) having a concentration of 5 gZL and a temperature of 40 ° C. for 1 minute, followed by washing with water.
  • the corrosion resistance is further improved by subjecting the surface of the aluminum material to anodic acid treatment, then sealing treatment, and then performing the surface chemical conversion treatment of the present invention.
  • the anodizing treatment and sealing treatment employed in the present invention are well known in the technical field, and well-known anodizing treatment technology and sealing treatment technology can be used as they are in the present invention.
  • anodic oxidation at a current density of 0.5 to 5 A / dm 2 and a bath temperature of 20 to 30 ° C for 10 to 30 minutes in a treatment solution having a sulfuric acid concentration of 1 to 5 molZL and a boric acid concentration of 0.1 to 0.3 mol / L is sealed by dipping in a treatment solution having a nickel acetate concentration of 1 to 5 gZL at a bath temperature of 85 ° C. for 2 to 10 minutes.
  • the treatment liquid used in the surface chemical conversion treatment method of the present invention contains chromium nitrate as an essential component.
  • Chromium nitrate is available as a 9-hydrate salt, an anhydrous salt, or a 40% by mass aqueous solution. Any product can be used in the present invention.
  • the concentration of chromium nitrate in the treatment solution is Cr (NO)
  • It is preferably 3-12gZL in terms of 100%, and should be about 4-10OZZL.
  • the concentration of chromium nitrate 9 hydrate is preferably about 4.2 to 20.lgZL.
  • the concentration of chromium nitrate in the treatment liquid is Cr (NO)
  • the concentration of chromium nitrate in the treatment liquid is 12 gZL as Cr (NO).
  • the treatment liquid used in the surface chemical conversion treatment method of the present invention contains ammonium vanadate as an essential component.
  • Ammonium vanadate - ⁇ beam is in a force present invention that are commercially available in as pure 98 mass 0/0 and 99 weight 0/0 can be used any product.
  • the concentration of ammonium vanadate in the treatment solution is 0.5-7 gZL in terms of NH VO 100%.
  • the treatment liquid used in the surface chemical conversion treatment method of the present invention contains titanium fluoride-containing rhodium as an essential component.
  • Potassium titanium fluoride is commercially available with a purity of 98% by mass or higher Any product can be used in the present invention.
  • the concentration of potassium titanium fluoride in the treatment solution should be 0.5 to 3 gZL in terms of K TiF 100%.
  • the concentration of titanium fluoride in the treatment liquid is less than 0.5 gZL as K TiF, the aluminum after chemical conversion treatment
  • the treatment liquid used in the surface chemical conversion treatment method of the present invention contains lithium fluoride as an essential component.
  • Lithium fluoride is commercially available with a purity of 99% by mass Any commercially available product can be used in the present invention.
  • the concentration of lithium fluoride in the treatment liquid is preferably about 0.5 to 3 gZL in terms of LiFl 00%, more preferably about 0.7 to 2.5 gZL.
  • concentration force SLiF of lithium fluoride in the treatment liquid is less than 0.5 gZL, the corrosion resistance of the surface of the aluminum material after the chemical conversion treatment tends to be insufficient.
  • the concentration of lithium fluoride in the treatment solution is higher than 3 gZL as LiF, no improvement in corrosion resistance is observed.
  • the treatment liquid used in the surface chemical conversion treatment method of the present invention contains nitric acid as an essential component.
  • Nitric acid is commercially available as an aqueous solution of 50% by volume, 62% by volume, 67.5% by volume, etc. Any product can be used in the present invention.
  • the concentration of nitric acid in the treatment solution is HNO 10
  • the treatment solution used in the surface chemical conversion treatment method of the present invention has the above-described yarn formation, its pH becomes weakly acidic.
  • the treatment liquid temperature is maintained at 40 to 50 ° C.
  • the liquid temperature is less than 40 ° C or when the liquid temperature exceeds 50 ° C, the corrosion resistance of the surface of the aluminum material after chemical conversion tends to be insufficient.
  • the chemical conversion treatment time is 1 to 5 minutes.
  • the corrosion resistance of the aluminum material surface after chemical conversion treatment tends to be insufficient.
  • the chemical conversion treatment time exceeds 5 minutes, no improvement in corrosion resistance can be seen.
  • the aluminum product having a coating film formed by the surface chemical conversion treatment method of the present invention is excellent in both corrosion resistance and adhesion of the coating film, and was treated by the chromate method and the phosphoric acid chromate method. Compared to the case, the same or better effect can be achieved.
  • test pieces obtained by die casting using ADC-12 alloy were immersed in an aqueous solution of Actan 70 (Meltex) at a liquid temperature of 40 ° C for 1 minute, and then at room temperature. Washing with tap water was performed for 30 seconds, followed by washing with pure water at room temperature for 30 seconds.
  • Actan 70 Meltex
  • the first table shows amounts of chromium nitrate-nonahydrate, 40 parts by mass 0/0 chromium sulfate (111), 99 mass 0/0 vanadate ammonium Yuumu, potassium 98 mass 0/0 titanium fluoride, 99 wt 0/0 lithium fluoride, 62 volume 0/0 processing solution 45 ° C containing nitrate ⁇ beauty 95 volume% sulfuric acid It was immersed in the solution for 3 minutes, followed by washing with tap water at room temperature for 30 seconds and then washing with pure water at room temperature for 30 seconds. Finally, drying was performed at 80 ° C for 20 minutes.
  • Example 1 and Example 2 show the results of performing twice under the same processing conditions.
  • Concentrations of essential components in the present invention shown in Table 1 are the molecular weight force S400 of chromium nitrate 9-hydrate, and the molecular weight of Cr (NO) is 238. Quantity lOgZL
  • the amount of ammonium phosphate 3gZL is 2.97gZL in terms of NH VO.
  • the amount of the amount 0/0 titanium fluoride Potassium lgZL is 0. 98GZL at concentrations as K TiF, 99
  • the mass% lithium fluoride concentration 2gZL is 1.89gZL as LiF, and the volume of 62vol% nitric acid 2mLZL is 1.24mLZL as HNO.
  • the corrosion resistance in the 96-hour salt spray test is 9.9 or higher in the rating number.
  • the corrosion resistance in the 24-hour salt spray test is 0.5 to 7.5 in the rating number.
  • the corrosion resistance in the 48 hour salt spray test was 6.0 as the rating number.
  • test pieces obtained by die casting using ADC-12 alloy were immersed in an aqueous solution of Actan 70 (Meltex) at a liquid temperature of 40 ° C for 1 minute, and then at room temperature. Washing with tap water was performed for 30 seconds, followed by washing with pure water at room temperature for 30 seconds.
  • Actan 70 Meltex
  • the sample was immersed in a 45 ° C treatment solution containing the concentrations shown in Table 3 for 3 minutes, and then washed with tap water at room temperature for 30 seconds, and then washed with pure water at room temperature for 30 seconds. Finally, drying was performed at 80 ° C for 20 minutes.
  • a large number of test pieces obtained by die casting using ADC-12 alloy were immersed in an aqueous solution of Actan 70 (Meltex) at a liquid temperature of 40 ° C for 1 minute, and then at room temperature. Washing with tap water was performed for 30 seconds, followed by washing with pure water at room temperature for 30 seconds. [0041] 95% by volume sulfuric acid was used as the sulfuric acid, 99.5% by weight boric acid was used as the boric acid, and 99% by weight nickel acetate tetrahydrate was used as the nickel acetate.
  • Specimens were anodized in a treatment solution with a sulfuric acid concentration of 2 molZL and boric acid concentration of 0.2 molZL for 20 minutes at a current density of 2AZ dm 2 and a bath temperature of 25 ° C. It was immersed and sealed at a bath temperature of 85 ° C for 5 minutes.
  • Example 2 The same conditions as in Example 1 were used, using six test pieces pretreated as described above and further subjected to anodizing treatment and sealing treatment as described above in each of Examples 26 and 27. Surface chemical conversion treatment was performed below.

Abstract

La présente invention concerne un procédé de traitement par conversion chimique de la surface d'un matériau en aluminium comprenant de l'aluminium ou un alliage d'aluminium. Le procédé comprend la réalisation d’un traitement par conversion chimique de la surface du matériau en aluminium avec une solution de traitement pendant 1 à 5 minutes de façon à former un film de revêtement ayant une excellente résistance à la corrosion et une excellente propriété d'adhérence au film de revêtement, la solution de traitement contenant un chrome trivalent et ayant une teneur en nitrate de chrome allant de 3 à 12 g/L en termes de Cr(NO3)3, une teneur en vanadate d'ammonium allant de 0,5 à 7 g/L en termes de NH4VO3, une teneur en fluorotitanate de potassium allant de 0,5 à 3 g/L en termes de K2TiF6, une teneur en fluorure de lithium allant de 0,5 à 3 g/L en termes de LiF, une teneur en acide nitrique allant de 0,5 à 1,8 mL/L en termes de HNO3 et une température du liquide allant de 40 à 50 °C. La présente invention concerne en outre un matériau en aluminium ayant un film de revêtement formé à l’aide du procédé.
PCT/JP2007/050077 2006-01-10 2007-01-09 Procede de traitement par conversion chimique de la surface d’un materiau en aluminium et materiau en aluminium WO2007080849A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN2007800011381A CN101356300B (zh) 2006-01-10 2007-01-09 铝材表面的化学转化处理方法及铝材
JP2007553897A JPWO2007080849A1 (ja) 2006-01-10 2007-01-09 アルミニウム材表面の化成処理方法及びアルミニウム材

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JP2006-003058 2006-01-10
JP2006003058 2006-01-10
JP2006-265778 2006-09-28
JP2006265778 2006-09-28

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EP2492371A1 (fr) * 2011-02-24 2012-08-29 Dr.Ing. Max Schlötter GmbH & Co. KG Solution de passivation sans cobalt et procédé de séparation de couches de passivation sans cobalt sur des surfaces de zinc et d'alliage de zinc
WO2014035690A1 (fr) * 2012-08-29 2014-03-06 Ppg Industries Ohio, Inc. Compositions de prétraitement du zirconium qui contiennent du lithium, procédés associés permettant de traiter des substrats métalliques et substrats métalliques recouverts associés
US10125424B2 (en) 2012-08-29 2018-11-13 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates
CN112725811A (zh) * 2020-11-27 2021-04-30 上海宏挺紧固件制造有限公司 一种大扁头螺丝及其加工方法
US11518960B2 (en) 2016-08-24 2022-12-06 Ppg Industries Ohio, Inc. Alkaline molybdenum cation and phosphonate-containing cleaning composition
WO2023119826A1 (fr) * 2021-12-22 2023-06-29 ディップソール株式会社 Liquide de traitement chimique et procédé de traitement chimique de matériau métallique cible

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CN105420714A (zh) * 2015-11-25 2016-03-23 广东致卓精密金属科技有限公司 高耐蚀性铝合金三价铬复合转化膜的制备方法
CN105463432A (zh) * 2015-12-31 2016-04-06 芜湖市金宇石化设备有限公司 一种铝合金表面磷化处理用处理液的制备方法
CN105463433A (zh) * 2015-12-31 2016-04-06 芜湖市金宇石化设备有限公司 一种铝合金表面磷化处理用处理液
CN105543833A (zh) * 2015-12-31 2016-05-04 芜湖市金宇石化设备有限公司 一种铝合金表面磷化处理方法
WO2018218428A1 (fr) * 2017-05-27 2018-12-06 深圳市恒兆智科技有限公司 Agent de formation de film, composant métallique, et procédé de traitement de formation de film de surface associé

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Cited By (10)

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Publication number Priority date Publication date Assignee Title
EP2492371A1 (fr) * 2011-02-24 2012-08-29 Dr.Ing. Max Schlötter GmbH & Co. KG Solution de passivation sans cobalt et procédé de séparation de couches de passivation sans cobalt sur des surfaces de zinc et d'alliage de zinc
WO2014035690A1 (fr) * 2012-08-29 2014-03-06 Ppg Industries Ohio, Inc. Compositions de prétraitement du zirconium qui contiennent du lithium, procédés associés permettant de traiter des substrats métalliques et substrats métalliques recouverts associés
RU2609585C2 (ru) * 2012-08-29 2017-02-02 Ппг Индастриз Огайо, Инк. Циркониевые композиции для предварительной обработки, содержащие литий, соответствующие способы обработки металлических субстратов и соответствующие металлические субстраты с покрытиями
US10125424B2 (en) 2012-08-29 2018-11-13 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates
US10400337B2 (en) 2012-08-29 2019-09-03 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing lithium, associated methods for treating metal substrates, and related coated metal substrates
US10920324B2 (en) 2012-08-29 2021-02-16 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates
US11518960B2 (en) 2016-08-24 2022-12-06 Ppg Industries Ohio, Inc. Alkaline molybdenum cation and phosphonate-containing cleaning composition
CN112725811A (zh) * 2020-11-27 2021-04-30 上海宏挺紧固件制造有限公司 一种大扁头螺丝及其加工方法
CN112725811B (zh) * 2020-11-27 2023-02-28 上海宏挺紧固件制造有限公司 一种大扁头螺丝及其加工方法
WO2023119826A1 (fr) * 2021-12-22 2023-06-29 ディップソール株式会社 Liquide de traitement chimique et procédé de traitement chimique de matériau métallique cible

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