EP3859053A1 - Verfahren zur dekorativen plattierung mit sulfatbasiertem, ammoniumfreiem trivalentem chrom - Google Patents

Verfahren zur dekorativen plattierung mit sulfatbasiertem, ammoniumfreiem trivalentem chrom Download PDF

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Publication number
EP3859053A1
EP3859053A1 EP20154909.4A EP20154909A EP3859053A1 EP 3859053 A1 EP3859053 A1 EP 3859053A1 EP 20154909 A EP20154909 A EP 20154909A EP 3859053 A1 EP3859053 A1 EP 3859053A1
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EP
European Patent Office
Prior art keywords
ions
bath
chromium
acid
group
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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.)
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EP20154909.4A
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English (en)
French (fr)
Inventor
Diego DAL ZILIO
Andrea Martin
Sandrine Dalbin
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Coventya SpA
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Coventya SpA
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
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Priority to EP20154909.4A priority Critical patent/EP3859053A1/de
Priority to CA3155524A priority patent/CA3155524C/en
Priority to PCT/EP2020/080584 priority patent/WO2021084103A1/en
Priority to JP2022521206A priority patent/JP7342253B2/ja
Priority to US17/755,503 priority patent/US20220403538A1/en
Priority to MX2022004290A priority patent/MX2022004290A/es
Priority to CN202080070306.8A priority patent/CN114729463A/zh
Priority to EP20796851.2A priority patent/EP4051829A1/de
Priority to KR1020227017823A priority patent/KR20220119012A/ko
Publication of EP3859053A1 publication Critical patent/EP3859053A1/de
Withdrawn legal-status Critical Current

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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
    • 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

Definitions

  • the present invention refers to an electroplating bath for electroplating a chromium or chromium alloy layer, the bath comprising trivalent chromium ions, organic carboxylic acid, sulfate ions, sodium conductive ions, and additives in the form of inorganic sulfur compound and boric acid as well as a process using such an electroplating bath.
  • Chrome deposits from trivalent chrome electrolytes are widely used in the industry due to their unique properties they allow substrates to work longer and under tougher conditions that they would normally survive in.
  • Decorative chrome plating is designed to be aesthetically pleasing and durable. Thicknesses range from 0.05 to 0.5 ⁇ m, however they are usually between 0.13 and 0.25 ⁇ m. Decorative chrome plating is also very corrosion resistant and is often used on car parts, tools and kitchen utensils.
  • hexavalent chrome deposits were featuring a blue-white appearance that is distinguishing from the trivalent chrome deposits. This colour is still very appreciated by customers that are used to hexavalent chrome products.
  • JP2009035806 describes a trivalent chromium plating bath and a method for producing a chromium plating.
  • This plating bath contains (1) complex solution of trivalent chromium obtained by maintaining under heating at least 1 type of component chosen from group which consists of aqueous solution aliphatic carboxylic acid and its salt, and aqueous solution containing trivalent chrome compound, (2) conductive salt (3) buffer for pH, and (4) at least 1 type of sulfur-containing compound chosen from the group having an SO2 group.
  • the drawback of such a plating solution is the use of a sulfur-containing organic compound instead of inorganic one and they do not use iron in the plating bath.
  • JP2010189673 describes novel trivalent chromium plating bath capable of forming a trivalent chromium plating film having better corrosion resistance as compared with the prior art.
  • a trivalent chromium plating bath comprising an aqueous solution containing a water-soluble trivalent chromium compound, a conductive salt, a pH buffer, a sulfur-containing compound and an aminocarboxylic acid.
  • the drawback of such a plating bath is the lack of sodium and iron ions in the plating bath which will not get the desired color.
  • WO2019117178 describes a trivalent chromium plating solution containing: a trivalent chromium compound; a complexing agent; potassium sulfate and ammonium sulfate as conductive salts; a pH buffer; and a sulfur-containing organic compound.
  • the trivalent chromium plating solution is practical and has a high plating deposition rate.
  • the drawback of such a plating solution is the use of a sulfur-containing organic compound instead of inorganic one and they do not use iron in the plating bath.
  • EP2411567 describes a chromium electroplating solution comprising a chromium electroplating solution comprising: (1) a water soluble trivalent chromium salt; (2) at least one complexant for trivalent chromium ions; (3) a source of hydrogen ions sufficient to create a pH of from 2.8-4.2; (4) a pH buffering compound; and (5) a sulfur-containing organic compound.
  • the chromium electroplating solution is usable in a method for producing an adherent metallic coating on a decorative article, such coating having enhanced resistance to corrosion in environments containing calcium chloride.
  • the drawback of such a solution is the use of a sulfur-containing organic compound instead of inorganic one and the absence of iron ions in the solution.
  • an electroplating bath for depositing a chromium or chromium alloy layer which comprises
  • the sulfate based trivalent chromium ions bath allows to obtain a whiter colour of the plating opposed to chloride based bath that get a darker plating with a higher carbon percentage.
  • the choice of the sodium is preferred to increase the whiteness of the plating.
  • the use of ferric or ferrous ions also increase the corrosion resistance permitting to pass the PV1073 A test.
  • the combination of ferric, sodium and sulfate ions permit to obtain a blue and white colour close to those from hexavalent chrome deposits.
  • an inorganic sulfur such as an oxyacid anion containing sulfur having the valence lower than 6 is preferred.
  • the degradation products of the organics sulfur compound cause chromability problems.
  • the advantage of the use of oxyacid anions containing sulfur is that they will produce sulfate as a degradation product, so it will not affect the plating bath as it already contains sulfate ions.
  • the at least one organic acid is selected from the group of dicarboxylic acids, preferably selected from the group consisting of malic acid, oxalic acid, succinic acid, glutaric acid, adipic acid, and mixtures thereof.
  • malic acid is selected from the group of dicarboxylic acids, preferably selected from the group consisting of malic acid, oxalic acid, succinic acid, glutaric acid, adipic acid, and mixtures thereof.
  • malic acid as organic acid.
  • the concentration of the at least one organic acid is from 5 to 40 g/L, preferably from 10 to 30 g/L, more preferably from 15 to 25 g/L.
  • the concentration of the at least one trivalent chromium ion is from 5 to 25 g/L, preferably from 8 to 20 g/L.
  • the concentration of the sulfate ions from at least one source of sulfate ions is from 150 to 300 g/L, preferably from 180 to 280 g/L, more preferably from 200 to 250 g/L.
  • the source of trivalent chromium ions is chromium(III) sulphate in acidic or basic form.
  • the at least one inorganic sulphur compound is an oxyacid anion containing sulfur having the valence lower than 6, selected from the group consisting of:
  • the concentration of the at least one inorganic sulfur compound is from 5 to 500 mg/L, preferably from 10 to 200 mg/L.
  • the concentration of the ferric or ferrous ions from at least one source of ferric or ferrous ions is preferably from 20 to 200 mg/L, more preferably from 30 to 150 mg/L, and even more preferably from 40 to 100 mg/L.
  • the concentration of the at least one pH buffer is in a range from 50 to 120 g/L, preferably from 60 to 110 g/L, more preferably from 80 to 100 g/L.
  • a pH buffer it is preferred to use at least one of the group boric acid, citric acid, succinic acid, lactic acid, tartaric acid, and mixtures thereof. Particular preffered is the use of boric acid as pH buffer.
  • the pH of the bath is preferably in the range from 1 to 5, more preferably from 2 to 4, and even more preferably from 3.1 to 3.9.
  • the concentration of the sodium vinyl sulfonate is preferably from 0.1 to 5 g/L, more preferably from 0.2 to 3 g/L.
  • the bath is (substantially) free of at least one of chloride ions, ammonium ions, amino carboxylic acid ions and hexavalent chromium ions. In particular, it is preferred that some or all of these ions are absent.
  • the concentration of sodium saccharin is from 0.1 to 10 g/L, and more preferably from 1 to 5 g/L.
  • the at least one inorganic sulfur compound is selected from the group of oxyacid anions comprising sulfur having a valence lower than 6, preferably selected from the group consisting of:
  • the at least one polyalkylene glycol has a molecular weight of lower than 2000 g/mol and is preferably selected from the group consisting of:
  • the concentration of the at least one polyalkylene glycol is from 1 to 15 g/L, preferably from 5 to 10 g/L.
  • a method for preparing an electroplated product by electroplating a substrate comprising the following steps:
  • the cathode current density is in a range from 3 to 14 A/dm 2 , preferably from 5 to 10, and/or the anode current density is in a range from 4 to 12 A/dm 2 , preferably from 5 to 10 A/dm 2 .
  • the anodes consist of a mixed metal oxide, preferably a mixed metal oxide selected from the group consisting of mixed metal oxides of at least two of platinum, ruthenium, iridium and tantalum, more preferably mixed metal oxides of iridium and tantalum.
  • the deposition rate during step C) is from 0.01 to 0.5 ⁇ m/min, preferably from 0.02 to 0.3 ⁇ m/min, and more preferably from 0.03 to 0.2 ⁇ m/min.
  • step C) is conducted at a temperature from 35 to 60°C, preferably from 40 to 58°C, more preferably from 45 to 55°C.
  • the alloy obtainable from this method comprises or consists of carbon, sulphur, oxygen, iron and chrome.
  • the alloy has a colour measured by L, a, b values from 80 to 86, -0.8 to 0, -0.7 to 1.0.
  • the L, a, b values are from 83 to 85, -0.7 to -0.4, -0.5 to 0.2.
  • the percentage of carbon in the alloy is preferably from 1 to 5 atomic % (at%), more preferably from 2 to 4at%.
  • the alloy preferably comprises from 0,5 to 4 at%, more preferably from 1 to 3 at% sulfur.
  • the alloy preferably comprises from 1 to 5 at%, preferably from 2 to 4 at% of oxygen. It is preferred, that the percentage of iron in the alloy is from 3 to 12 at%, preferably from 5 to 10 at%.
  • the alloy preferably comprises from 74 to 94.5 at%, more preferably from 79 to 90 at% chrome.
  • Fig.1 shows the chromium coverage on a Hull cell panel with the three points (HCD, MCD, LCD) used for the examples.
  • the panels were evaluated: the thickness of Chromium using the X-Ray method EN ISO 3497 in three points 1cm from the left edge define as HCD (High Current Density), 5 cm from the left edge define as MCD (Medium Current Density), 7 cm from the left edge define as LCD (Low Current Density).
  • HCD High Current Density
  • MCD Medium Current Density
  • LCD Low Current Density
  • the point defined as MCD was evaluated the colour by a Colorimeter KONICA MINOLTA CM2600 defining the colour as CIELAB (L, a, b).
  • Chromium deposit coverage measuring the mm from the left edge to the maximum coverage of the deposit to the right.
  • Chromium deposit was tested to the PV1073 A that is a automotive standard used to evaluate the corrosion performance of Chromium deposit to the Calcium Chloride.
  • n°1 are summarized the examples results.
  • the table shows how each component has a different effect in terms of: thicknesses, coverage, color and performance versus PV 1073 A corrosion test.
  • the present invention refers to the alloy carried out with the example n°6 characterized in that the alloy composition contains 5-10 at % of Fe, 1-3 at % of S, 2-4 at % of C, 2-4 at % of O, remaining at % Cr (up to 100 at %) and reaching a comparable color to the reference example and a good deposition rate, with the features of claim 1 and the method for preparing an electroplated product by using the electroplating bath with the features of claim 10.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
EP20154909.4A 2019-10-31 2020-01-31 Verfahren zur dekorativen plattierung mit sulfatbasiertem, ammoniumfreiem trivalentem chrom Withdrawn EP3859053A1 (de)

Priority Applications (9)

Application Number Priority Date Filing Date Title
EP20154909.4A EP3859053A1 (de) 2020-01-31 2020-01-31 Verfahren zur dekorativen plattierung mit sulfatbasiertem, ammoniumfreiem trivalentem chrom
CA3155524A CA3155524C (en) 2019-10-31 2020-10-30 Sulfate based, ammonium free trivalent chromium decorative plating process
PCT/EP2020/080584 WO2021084103A1 (en) 2019-10-31 2020-10-30 Sulfate based, ammonium free trivalent chromium decorative plating process
JP2022521206A JP7342253B2 (ja) 2019-10-31 2020-10-30 硫酸系、アンモニア不含三価クロム装飾めっきプロセス
US17/755,503 US20220403538A1 (en) 2019-10-31 2020-10-30 Sulfate based, ammonium free trivalent chromium decorative plating process
MX2022004290A MX2022004290A (es) 2019-10-31 2020-10-30 Proceso de enchapado decorativo con cromo trivalente libre de amonio, a base de sulfato.
CN202080070306.8A CN114729463A (zh) 2019-10-31 2020-10-30 基于硫酸根的无铵的三价铬装饰性镀覆工艺
EP20796851.2A EP4051829A1 (de) 2019-10-31 2020-10-30 Verfahren zur dekorativen plattierung mit sulfatbasiertem, ammoniumfreiem trivalentem chrom
KR1020227017823A KR20220119012A (ko) 2019-10-31 2020-10-30 설페이트계 암모늄 무함유 3가 크롬 장식 도금 공정

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Application Number Priority Date Filing Date Title
EP20154909.4A EP3859053A1 (de) 2020-01-31 2020-01-31 Verfahren zur dekorativen plattierung mit sulfatbasiertem, ammoniumfreiem trivalentem chrom

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EP3859053A1 true EP3859053A1 (de) 2021-08-04

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61235592A (ja) * 1985-02-06 1986-10-20 ダブリユ−　キヤニング　マテリアルズ　リミテツド 改良された電気メツキ方法
US5196109A (en) * 1991-08-01 1993-03-23 Geoffrey Scott Trivalent chromium electrolytes and plating processes employing same
EP1845176A1 (de) * 2004-10-18 2007-10-17 Yamaha Hatsudoki Kabushiki Kaisha Motorteil
JP2009035806A (ja) 2007-07-12 2009-02-19 Okuno Chem Ind Co Ltd ３価クロムめっき浴及びその製造方法
JP2010189673A (ja) 2009-02-16 2010-09-02 Okuno Chem Ind Co Ltd ３価クロムめっき浴
EP2411567A1 (de) 2009-03-24 2012-02-01 MacDermid Acumen, Inc. Chormlegierungsüberzug mit verbesserter beständigkeit gegenüber korrosion in calciumchlorid-umgebungen
WO2019117178A1 (ja) 2017-12-13 2019-06-20 株式会社Ｊｃｕ ３価クロムメッキ液およびこれを用いたクロムメッキ方法
US20190203360A1 (en) * 2016-09-27 2019-07-04 Atotech Deutschland Gmbh Method for treatment of a chromium finish surface

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61235592A (ja) * 1985-02-06 1986-10-20 ダブリユ−　キヤニング　マテリアルズ　リミテツド 改良された電気メツキ方法
US5196109A (en) * 1991-08-01 1993-03-23 Geoffrey Scott Trivalent chromium electrolytes and plating processes employing same
EP1845176A1 (de) * 2004-10-18 2007-10-17 Yamaha Hatsudoki Kabushiki Kaisha Motorteil
JP2009035806A (ja) 2007-07-12 2009-02-19 Okuno Chem Ind Co Ltd ３価クロムめっき浴及びその製造方法
JP2010189673A (ja) 2009-02-16 2010-09-02 Okuno Chem Ind Co Ltd ３価クロムめっき浴
EP2411567A1 (de) 2009-03-24 2012-02-01 MacDermid Acumen, Inc. Chormlegierungsüberzug mit verbesserter beständigkeit gegenüber korrosion in calciumchlorid-umgebungen
US20190203360A1 (en) * 2016-09-27 2019-07-04 Atotech Deutschland Gmbh Method for treatment of a chromium finish surface
WO2019117178A1 (ja) 2017-12-13 2019-06-20 株式会社Ｊｃｕ ３価クロムメッキ液およびこれを用いたクロムメッキ方法

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