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WO2023120954A1 - Procédé de passivation d'article revêtu par injection - Google Patents

Procédé de passivation d'article revêtu par injection Download PDF

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Publication number
WO2023120954A1
WO2023120954A1 PCT/KR2022/016914 KR2022016914W WO2023120954A1 WO 2023120954 A1 WO2023120954 A1 WO 2023120954A1 KR 2022016914 W KR2022016914 W KR 2022016914W WO 2023120954 A1 WO2023120954 A1 WO 2023120954A1
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WO
WIPO (PCT)
Prior art keywords
passivation
injection
plating
injection molding
plated
Prior art date
Application number
PCT/KR2022/016914
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English (en)
Korean (ko)
Inventor
이경환
고영덕
김광주
김진주
Original Assignee
삼성전자주식회사
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 삼성전자주식회사 filed Critical 삼성전자주식회사
Publication of WO2023120954A1 publication Critical patent/WO2023120954A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/024—Anodisation under pulsed or modulated current or potential
    • 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
    • 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
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/38—Chromatising
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/04—Electroplating: Baths therefor from solutions of chromium
    • C25D3/06—Electroplating: Baths therefor from solutions of chromium from solutions of trivalent chromium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • C25D5/56—Electroplating of non-metallic surfaces of plastics

Definitions

  • the present invention relates to a passivation treatment method for an injection-plated product, and more particularly, to a passivation treatment method for an injection-plated product for improving corrosion resistance and chemical resistance by passivation treatment.
  • chrome plating is to visually enhance aesthetics, and functionally to cathode the material through a passivation film to create an electrochemically inactive state to increase corrosion resistance and abrasion resistance.
  • This naturally generated passivation film exists on the surface layer as very thin as 1-3 nm.
  • Types of chromium plating currently commercialized include trivalent chromium plating and hexavalent chromium plating.
  • trivalent chromium plating is gradually being regulated globally as carcinogens, and trivalent chromium plating is increasing as an alternative.
  • trivalent chromium plating is significantly inferior to hexavalent chromium in corrosion resistance and chemical resistance.
  • the trivalent chromium plating is plated at a high current density, microcracks due to internal stress may exist, and water or oxygen comes into contact with the nickel plating layer, which is an underlying layer, through the microcracks. Accordingly, a local battery in which the nickel plating layer serves as an anode is formed to promote corrosion.
  • iron (Fe) is used as a conduction aid, and the iron component forms vacancies in the plating layer to promote corrosion.
  • transparent coating is applied after trivalent chromium plating in order to prevent the above-mentioned defects, but a lot of money loss occurs due to cost increase and defect rate increase due to coating cost.
  • An object of the present invention to solve the above problems is to provide a passivation treatment method for an injection-plated material that improves corrosion resistance and chemical resistance through a passivation process while utilizing trivalent chromium plating.
  • a passivation treatment method for an injection-plated article includes the steps of racking and degreasing the injection-molded article; Etching and neutralizing the degreased injection product; Catalyzing and accelerating the neutralized injection molding product; plating the accelerated injection molding; Passivating the plated injection molding; and drying, wherein the plating step includes trivalent chromium plating, and the passivating step may be performed using Pulse Reverse Current (PR).
  • PR Pulse Reverse Current
  • the plating step may include chemical nickel plating.
  • the plating may include copper plating.
  • the plating step may include nickel plating.
  • the passivation step is composed of 1 to 3% of Chromium (III) sulfate, 5 to 10% of Etidronic acid, and 87 to 94% of distilled water as main components It can be carried out with a passivation solution containing
  • the passivation step may be performed with a passivation liquid containing 3,3'-Methylenebis as an additive.
  • the passivation step may be performed with a passivation liquid containing an organic salt.
  • the passivation step may apply a current density of 0.1 to 0.4 A/dm 2 .
  • the passivation step may be performed with a passivation liquid having a pH of 9.3 to 9.7 and a temperature of 25 to 35 °C.
  • the passivation step may be performed for 210 to 240 seconds.
  • the drying step may be performed at 60 to 70° C. for 5 to 10 minutes.
  • the passivation treatment method of the injection-plated article according to an embodiment of the present invention may further include a step of washing the water after the passivation step.
  • the washing step may be performed by immersing in ion-exchanged water or distilled water at 40 to 60 ° C. for 30 to 90 seconds.
  • the thickness of the passivation film generated through the passivation treatment method of injection-plated material according to an embodiment of the present invention may be 8 nm or more.
  • the passivation treatment method of injection molding includes the steps of racking and degreasing the injection molding; Etching and neutralizing the degreased injection product; Catalyzing and accelerating the neutralized injection molding product; plating the accelerated injection molding; Passivating the plated injection molding; and drying, and the resulting passivation film may have a thickness of 8 nm or more.
  • injection molding according to an embodiment of the present invention, the injection molding; a plating layer provided on the injection-molded product; and a passivation film provided on the plating layer, wherein the plating layer includes trivalent chromium plating, and the passivation film may have a thickness of 8 nm or more.
  • FIG. 1 is a flow chart showing a passivation treatment method for an injection-plated product according to an example of the present invention.
  • FIG. 2 is a schematic diagram showing the occurrence of corrosion due to micro cracks and surface vacancies present in a plated product subjected to trivalent chromium plating.
  • FIG 3 is a cross-sectional photograph of micro-cracks present in a plated product subjected to trivalent chromium plating using a scanning electron microscope (SEM).
  • FIG. 4 is a schematic diagram showing an injection-plated material subjected to passivation treatment according to an embodiment of the present invention.
  • FIG. 5 is a graph showing the thickness of the passivation film subjected to the passivation process using a general DC current.
  • FIG. 6 is a graph showing the thickness of a passivation film subjected to passivation treatment using a PR current.
  • FIG. 7 is a photograph showing poor rusting as a result of performing a 72-hour salt spray test on a plated product plated with trivalent chromium.
  • FIG. 8 is a photograph showing defects in blistering as a result of performing a 72-hour salt spray test on a plate plated with trivalent chromium.
  • FIG. 9 is a photograph showing no defects as a result of performing a 120-hour salt spray test, a 96-hour detergent test, and a 3-hour bleach test on the passivated injection molding according to an example of the present invention.
  • FIG. 10 is a photograph showing poor rusting as a result of performing a 24-hour detergent test on a plate plated with trivalent chromium.
  • FIG. 11 is a photograph showing peeling defects as a result of performing a 2-hour lax test on a plated material plated with trivalent chromium.
  • a passivation treatment method for an injection-plated article includes the steps of racking and degreasing the injection-molded article; Etching and neutralizing the degreased injection product; Catalyzing and accelerating the neutralized injection molding product; plating the accelerated injection molding; Passivating the plated injection molding; and drying, wherein the plating step includes trivalent chromium plating, and the passivating step may be performed using Pulse Reverse Current (PR).
  • PR Pulse Reverse Current
  • a passivation treatment method for an injection-plated article includes the steps of racking and degreasing the injection-molded article; Etching and neutralizing the degreased injection product; Catalyzing and accelerating the neutralized injection molding product; plating the accelerated injection molding; Passivating the plated injection molding; and drying.
  • FIG. 1 is a flow chart showing a passivation treatment method for an injection-plated product according to an example of the present invention.
  • a passivation treatment method for an injection-plated article may include steps of racking, degreasing, etching, neutralization, catalization, acceleration, plating, passivation, and drying. Each step is described in detail below.
  • the plastic material may be ABS or PC-ABS material, but is not limited thereto.
  • the plastic material may be manufactured as an injection molding product by injection molding according to the purpose.
  • a degreasing step for removing foreign substances from the injection-molded product may be performed.
  • the degreasing step may be performed by immersing the injection-molded product in a degreasing agent at 45 to 55° C. for 1 to 5 minutes.
  • the degreased injection molding product may generate an anchor by performing an etching step to remove the butadiene component on the surface.
  • the etching process may be performed by immersing for 8 to 12 minutes in a mixed solution containing 380 to 420 g/L of chromic anhydride and 200 to 240 ml/L of sulfuric acid at 68 to 70 °C.
  • a step of neutralizing the etching solution may be performed to prevent non-plating.
  • the neutralization step may be performed by immersing in a solution containing 30 to 35 ml/L of hydrochloric acid at 20 to 30° C. for 1 to 2 minutes.
  • a catalysing step for adsorbing Pd (palladium) and Sn (tin) components to the surface of the neutralized injection molding product may be performed.
  • the catalyzing step may be performed by immersing for 2 to 3 minutes in a mixed solution containing 50 ppm in Pd 30 and 200 to 300 ml / L of hydrochloric acid at 27 to 33 ° C.
  • the Catalyst injection molding product undergoes an Acceleration step, whereby the Sn (tin) component adsorbed in the Catalyst process can be removed.
  • the accelerating step may be performed by immersing in a solution containing 180 to 220 ml/L of sulfuric acid at 40 to 50° C. for 2 to 3 minutes.
  • a step of plating the accelerated injection-molded product may be performed.
  • the plating may include chemical nickel plating, copper plating, nickel plating, and trivalent chromium plating.
  • the chemical nickel plating is a process of forming an electroless nickel plating layer so that electricity can be applied using the Pd (palladium) component on the surface of the injection molding product as a catalyst. That is, the chemical nickel plating can be regarded as a preceding process for electroplating. According to one example of the present invention, the chemical nickel plating may be performed by dipping for 5 to 8 minutes in a solution containing 5 to 10 g/L of nickel sulfate and 12 to 18 g/L of hypophosphite at 25 to 45 ° C. .
  • the copper plating is a process of forming a copper plating layer on the surface of an injection-molded product so as to perform a role of imparting gloss through surface smoothing and buffering between the injection-molded product and the Ni (nickel) plating layer.
  • the copper plating may be performed with a solution containing 180 to 220 g/L of copper sulfate, 50 to 70 g/L of sulfuric acid, and additives at 22 to 30°C.
  • the copper plating layer formed through the copper plating may have a thickness of 15 ⁇ m or more.
  • the nickel plating is a process of forming a nickel plating layer on top of the copper plating layer in order to impart corrosion resistance and surface gloss to the injected product.
  • the nickel plating may be performed with a solution containing 250 to 280 g/L of nickel sulfate, 40 to 60 g/L of nickel chloride, and additives at 45 to 55 °C.
  • a thickness of the nickel plating layer formed through the nickel plating may be 10 ⁇ m or more.
  • the trivalent chromium plating is a process of forming a trivalent chromium plating layer on top of the nickel plating layer in order to improve corrosion resistance and surface hardness of an injection-molded product.
  • the trivalent chromium plating may be performed with a solution containing 100 to 120 g/L of chromium chloride and an additive at 20 to 30°C.
  • the trivalent chromium plating layer formed through the trivalent chromium plating may have a thickness of 0.15 ⁇ m or more.
  • a step of passivating the plated injection molding product may be performed.
  • the passivation liquid used in the passivation treatment step may include, as main components, 1 to 3% of Chromium (III) sulfate, 5 to 10% of Etidronic acid, and 87 to 94% of distilled water.
  • main components etidronic acid can play a role in adjusting the pH of the passivation solution.
  • the main component may be added in an amount of 23 to 27ml/L.
  • the passivation solution used in the passivation treatment step may contain 3,3'-Methylenebis as an additive.
  • the additive may serve to prevent trivalent chromium from being oxidized to hexavalent chromium.
  • the additive may be added in an amount of 0.3 to 0.7ml/L.
  • the passivation liquid used in the passivation treatment step may contain an organic salt.
  • the organic salt may include, for example, a surfactant.
  • the organic salt may play a role of increasing the reaction rate by lowering the surface tension, allowing the passivation liquid to spread uniformly on the surface of the injection-molded product.
  • the organic salt may be added in an amount of 14 to 16 g/L.
  • the passivating step may be performed with a passivation liquid having a pH of 9.3 to 9.7 and a temperature of 25 to 35 °C.
  • the above pH and temperature ranges are ranges in which a thick passivation film can be formed within a range that does not reduce productivity.
  • the passivating step may be performed for 210 to 240 seconds.
  • the passivation treatment time is short, the passivation film may be formed thinly.
  • the passivation treatment is performed for a long time, it may be difficult to secure sufficient corrosion resistance and chemical resistance.
  • the passivation process may be performed using Pulse Reverse Current (PR).
  • PR Pulse Reverse Current
  • the corrosion resistance of metal depends on how dense and chemically stable the oxide film formed on the metal surface is.
  • the PR current does not have a large current deviation between high current and low current, so it can play a role in forming a uniform and dense passivation film.
  • a current density of 0.1 to 0.4 A/dm 2 may be applied using an injection-molded product as a cathode.
  • the current density range may be set in consideration of productivity and passivation film thickness.
  • the drying step may be performed at 60 to 70° C. for 5 to 10 minutes.
  • the passivation treatment method of injection molding according to an embodiment of the present invention may further include a step of washing the water after the passivation step.
  • the rinsing may be performed to efficiently perform a drying process by removing chromic acid and organic substances, which are harmful components, remaining on the surface of the injection-molded product and removing moisture from the surface of the injection-molded product.
  • the step of washing the water may be performed by immersing in ion-exchanged water or distilled water at 40 to 60 ° C. for 30 to 90 seconds.
  • the thickness of the passivation film created through the passivation treatment method of the injection-plated material described above may be 8 nm or more.
  • the thickness of the passivation film that is naturally generated is 1 to 3 nm, and the thickness of the passivation film that is generated through a general DC current is about 3 nm. Therefore, corrosion resistance and chemical resistance can be improved by forming a uniform and thick passivation film through the passivation treatment method of injection molding according to one embodiment of the present invention.
  • An injection-plated product is an injection-molded product; a plating layer provided on the injection-molded product; and a passivation film provided on the plating layer, wherein the plating layer includes trivalent chromium plating, and the passivation film may have a thickness of 8 nm or more.
  • the plating layer may include a copper plating layer, a nickel plating layer, and a trivalent chromium plating layer.
  • FIG. 2 is a schematic diagram showing the occurrence of corrosion due to microcracks and surface vacancies present in a plating material plated with trivalent chromium
  • FIG. 3 shows microcracks present in a plating material plated with trivalent chromium using a scanning electron microscope (SEM) , a cross-sectional picture taken with a scanning electron microscope).
  • SEM scanning electron microscope
  • FIG. 4 is a schematic diagram showing an injection-plated material subjected to passivation treatment according to an embodiment of the present invention.
  • the resulting passivation film thickness was measured through XPS analysis.
  • a salt spray test, a detergent test, and a lax test are performed to determine corrosion resistance and chemical resistance. Evaluated.
  • XPS X-ray Photoelectron. Spectroscopy
  • FIG. 5 is a graph showing the thickness of the passivation film passivated using a general DC current
  • FIG. 6 is a graph showing the thickness of the passivation film subjected to the passivation process using a PR current.
  • the salt spray test was performed over a certain cycle by spraying 5 wt% sodium chloride (NaCl) for 8 hours and resting for 16 hours as one cycle at a temperature of 35 ° C.
  • FIG. 7 is a photograph showing poor rusting as a result of performing a 72-hour salt spray test on a plate plated with trivalent chromium
  • FIG. 8 is a 72-hour salt spray test for a plate plated with trivalent chromium.
  • FIG. 9 is a 120-hour salt spray test, a 96-hour detergent test, and a 3-hour bleach test for the passivated injection plating material according to an example of the present invention, respectively. As a result, it is a picture without defects.
  • the detergent test was carried out by immersion in a 60° C. solution of 0.5% bleach, 0.5% detergent and the rest distilled water for a certain period of time or longer.
  • FIG. 10 is a photograph showing poor rusting as a result of performing a 24-hour detergent test on a plating material plated with trivalent chromium, and FIG. As a result of performing a 120-hour salt spray test, a 96-hour detergent test, and a 3-hour bleach test, respectively, this is a photo showing no defects.
  • the lacquer test was performed by immersing 5% lacquer at room temperature for a certain period of time or longer.
  • FIG. 11 is a photograph showing peeling defects as a result of performing a 2-hour bleach test on a plating material plated with trivalent chromium, and FIG. As a result of performing a 120-hour salt spray test, a 96-hour detergent test, and a 3-hour bleach test, respectively, this is a photo showing no defects.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Chemically Coating (AREA)

Abstract

Un procédé pour la passivation d'un article revêtu par injection, selon un mode de réalisation de la présente invention, comprend les étapes consistant à : soutirer et dégraisser l'article moulé par injection ; graver et neutraliser l'article moulé par injection dégraissé ; catalyser et accélérer l'article moulé par injection neutralisé ; revêtir l'article moulé par injection accéléré ; passiver l'article moulé par injection revêtu ; et sécher celui-ci, l'étape de revêtement consistant à revêtir avec du chrome trivalent et l'étape de passivation étant effectuée à l'aide d'un courant à impulsions inversées (PR).
PCT/KR2022/016914 2021-12-21 2022-11-01 Procédé de passivation d'article revêtu par injection WO2023120954A1 (fr)

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KR10-2021-0184248 2021-12-21
KR1020210184248A KR20230094811A (ko) 2021-12-21 2021-12-21 사출 도금물의 부동태 처리 방법

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015209579A (ja) * 2014-04-28 2015-11-24 ユケン工業株式会社 着色部材およびその製造方法、液状電解質ならびに濃縮組成物
JP2019108616A (ja) * 2014-03-07 2019-07-04 マクダーミッド アキューメン インコーポレーテッド 三価電解液から析出される微小不連続クロムの不動態化
KR20200014970A (ko) * 2018-08-02 2020-02-12 주식회사 주영테크 도금 불량 방지기능을 갖는 이중 사출 성형품의 도금방법
JP2020506292A (ja) * 2017-02-13 2020-02-27 アトテツク・ドイチユラント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツングＡｔｏｔｅｃｈ Ｄｅｕｔｓｃｈｌａｎｄ ＧｍｂＨ 最外クロム層または最外クロム合金層を電解不動態化して耐食性を向上させる方法
US20200340122A1 (en) * 2019-04-26 2020-10-29 Bulk Chemicals, Inc. Process and composition for passivating metal surfaces

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019108616A (ja) * 2014-03-07 2019-07-04 マクダーミッド アキューメン インコーポレーテッド 三価電解液から析出される微小不連続クロムの不動態化
JP2015209579A (ja) * 2014-04-28 2015-11-24 ユケン工業株式会社 着色部材およびその製造方法、液状電解質ならびに濃縮組成物
JP2020506292A (ja) * 2017-02-13 2020-02-27 アトテツク・ドイチユラント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツングＡｔｏｔｅｃｈ Ｄｅｕｔｓｃｈｌａｎｄ ＧｍｂＨ 最外クロム層または最外クロム合金層を電解不動態化して耐食性を向上させる方法
KR20200014970A (ko) * 2018-08-02 2020-02-12 주식회사 주영테크 도금 불량 방지기능을 갖는 이중 사출 성형품의 도금방법
US20200340122A1 (en) * 2019-04-26 2020-10-29 Bulk Chemicals, Inc. Process and composition for passivating metal surfaces

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