EP0737760A1 - Platinum electroplating bath - Google Patents

Platinum electroplating bath Download PDF

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Publication number
EP0737760A1
EP0737760A1 EP96102799A EP96102799A EP0737760A1 EP 0737760 A1 EP0737760 A1 EP 0737760A1 EP 96102799 A EP96102799 A EP 96102799A EP 96102799 A EP96102799 A EP 96102799A EP 0737760 A1 EP0737760 A1 EP 0737760A1
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EP
European Patent Office
Prior art keywords
acid
platinum
complex
amine
bath
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.)
Granted
Application number
EP96102799A
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German (de)
French (fr)
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EP0737760B1 (en
Inventor
Werner Kuhn
Wolfgang Zilske
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.)
Evonik Operations GmbH
Original Assignee
Degussa GmbH
Degussa Huels AG
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Publication date
Priority claimed from DE19547900A external-priority patent/DE19547900C2/en
Application filed by Degussa GmbH, Degussa Huels AG filed Critical Degussa GmbH
Publication of EP0737760A1 publication Critical patent/EP0737760A1/en
Application granted granted Critical
Publication of EP0737760B1 publication Critical patent/EP0737760B1/en
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Expired - Lifetime legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/50Electroplating: Baths therefor from solutions of platinum group metals

Definitions

  • the invention relates to a galvanic platinum bath, in particular for the deposition of thick layers, which contains 5 to 30 g / l of platinum as amine sulfamato complex and has a pH of less than 1.
  • Acidic and alkaline baths based on platinum (II) and platinum (IV) compounds are used for the galvanic deposition of platinum.
  • the most important bath types contain diamminodinitritoplatinic acid (II) (P salt), sulfatodinitritoplatinic acid (DNS) or hexahydroxoplatinic acid, or their alkali salts.
  • the bath types mentioned are mainly only suitable for the deposition of thin platinum layers of a few ⁇ m.
  • the deposition of thick layers for technical applications is a general problem with platinum. Either the layers have high internal stresses, become cracked and even burst, or the electrolytes are not sufficiently stable and decompose relatively quickly during the long electrolysis times.
  • an acid bath for the electrodeposition of platinum coatings which consists of an aqueous solution of a complex dinitroplatinate (II) compound and has a pH below 2.
  • the dinitrosulfamato complex can also be used as a complex platinum compound. According to their own information, these platinum baths only give layers up to 25 ⁇ m thick. Layers over 25 ⁇ m tend to crack and are therefore not suitable for many applications.
  • DE-PS 12 56 992 describes a galvanic platinum bath which consists of an aqueous solution of Platinum diamminodinitrite (P salt) and alkali metal salts of sulfamic acid exist and are operated at pH values from 6.5 to 8. Here, too, you get only layer thicknesses of up to about 20 ⁇ m. However, the pH must be kept constant within narrow limits. At pH values below 3, the platinum layer will come off again.
  • P salt Platinum diamminodinitrite
  • alkali metal salts of sulfamic acid exist and are operated at pH values from 6.5 to 8.
  • P salt Platinum diamminodinitrite
  • alkali metal salts of sulfamic acid exist and are operated at pH values from 6.5 to 8.
  • the pH must be kept constant within narrow limits. At pH values below 3, the platinum layer will come off again.
  • the P salt is reacted with a large excess of sulfamic acid, NH 2 SO 3 H, so that a diluted bath with 6-20 g / l platinum and 20 Contains -100 g / l sulfamic acid (amidosulfuric acid).
  • this electrolyte is only stable as long as the bath is in operation. Thick layers can only be obtained without cracks with a matt surface.
  • the electrolyte contains at most 5 g / l of free amidosulfuric acid (sulfamic acid) and 20 to 400 g / l of a strong acid with a pH value less than 1.
  • Sulfuric acid, methanesulfonic acid or perchloric acid is preferably used as the strong acid.
  • other mineral acids such as fluorosulfuric acid or fluoroboric acid, alkanesulfonic acids, such as methanedisulfonic acid, ethanesulfonic acid, hydroxyethanesulfonic acid and homologues, or perfluorinated alkanesulfonic acids, such as trifluoromethanesulfonic acid or pentafluoroethanesulfonic acid, and perfluorocarboxylic acids, such as trifluoroacetic acid, can also be used.
  • the electrolyte additionally contains 0.01 to 0.2 g / l of a fluorosurfactant as a wetting agent.
  • the bath may also contain 0.01-0.2 g / l of a fluorosurfactant to suppress spray. It is operated at a temperature between 60 and 90 ° C and at current densities of 1-4 A / dm 2 .
  • the platinum amine sulfamato complex solution proved to be surprisingly stable in the strongly acidic bath without free amidosulfuric acid.
  • the bath showed no precipitation even with long electrolysis times.
  • sulfamate is rapidly hydrolyzed and does not accumulate in the electrolyte.
  • the platinum coatings deposited from these baths are crack-free, shiny and ductile even with layer thicknesses over 100 ⁇ m.
  • a galvanic platinum bath is prepared as follows: 80 ml of sulfuric acid (97%) are diluted in approx. 600 ml of water. This solution contains 16 g of platinum in the form of Platinum amine sulfamato complex solution and 0.1 g of a fluorosurfactant added. After filling with water, 1 l of the finished bath is obtained. At a bath temperature of 80 ° C and a current density of 2 A / dm 2 , a part made of silver is coated while rotating. After approx. 13 hours, an approx. 120 ⁇ m thick, shiny platinum layer has deposited evenly. After removing the silver with nitric acid, diluted 1: 1, a stable, crack-free platinum foil is obtained.

Abstract

Platinum electroplating bath, esp. for depositing thick layers, contains 5-30 g/l Pt as an amine sulphamate complex and has pH less than 1, the novelty being that the electrolyte contains max. 5 g/l free amido-sulphuric acid, 20-400 g/l strong acid (pref. sulphuric acid, methane-sulphonic acid or perchloric acid) with pH less than 1 and pref. 0.01-0.2 g/l fluorine-contg. surfactant as wetting agent. Pref. the amine sulphamate complex is the product of reaction of 1 mol. Pt(II) diamine di:nitrite with 4-6 mol. amidosulphuric acid.

Description

Die Erfindung betrifft ein galvanisches Platinbad, insbesondere zur Abscheidung dicker Schichten, das 5 bis 30 g/l Platin als Amminsulfamato-Komplex enthält und einen pH-Wert von weniger als 1 aufweist.The invention relates to a galvanic platinum bath, in particular for the deposition of thick layers, which contains 5 to 30 g / l of platinum as amine sulfamato complex and has a pH of less than 1.

Für die galvanische Abscheidung von Platin werden saure und alkalische Bäder auf der Basis von Platin(II)- und Platin(IV)-Verbindungen verwendet. Die wichtigsten Badtypen enthalten Diamminodinitritoplatin(II) (P-Salz), Sulfatodinitritoplatinsäure (DNS) oder Hexahydroxoplatinsäure, beziehungsweise deren Alkalisalze. Die genannten Badtypen eignen sich überwiegend nur für die Abscheidung dünner Platinschichten von wenigen µm. Die Abscheidung dicker Schichten für technische Anwendungen ist bei Platin ein generelles Problem. Entweder die Schichten haben hohe innere Spannungen, werden rissig und platzen sogar auf, oder die Elektrolyte sind nicht ausreichend stabil und zersetzen sich bei den langen Elektrolysezeiten relativ rasch.Acidic and alkaline baths based on platinum (II) and platinum (IV) compounds are used for the galvanic deposition of platinum. The most important bath types contain diamminodinitritoplatinic acid (II) (P salt), sulfatodinitritoplatinic acid (DNS) or hexahydroxoplatinic acid, or their alkali salts. The bath types mentioned are mainly only suitable for the deposition of thin platinum layers of a few µm. The deposition of thick layers for technical applications is a general problem with platinum. Either the layers have high internal stresses, become cracked and even burst, or the electrolytes are not sufficiently stable and decompose relatively quickly during the long electrolysis times.

Aus der DE-PS 11 82 924 ist ein saures Bad zum galvanischen Abscheiden von Platinüberzügen bekannt, das aus einer wässrigen Lösung einer komplexen Dinitroplatinat(II)-Verbindung besteht und einen pH-Wert unter 2 aufweist. Als komplexe Platinverbindung kann auch der Dinitrosulfamatokomplex eingesetzt werden. Nach eigenen Angaben erhält man mit diesen Platinbädern nur Schichtdicken bis zu 25 µm. Schichten über 25 µm neigen zum Reißen und sind daher für viele Anwendungen nicht geeignet.From DE-PS 11 82 924 an acid bath for the electrodeposition of platinum coatings is known, which consists of an aqueous solution of a complex dinitroplatinate (II) compound and has a pH below 2. The dinitrosulfamato complex can also be used as a complex platinum compound. According to their own information, these platinum baths only give layers up to 25 µm thick. Layers over 25 µm tend to crack and are therefore not suitable for many applications.

In der DE-PS 12 56 992 wird ein galvanisches Platinbad beschrieben, das aus einer wässrigen Lösung von Platindiamminodinitrit (P-Salz) und Alkalisalzen der Sulfamidsäure besteht und bei pH-Werten von 6,5 bis 8 betrieben wird. Auch hier bekommt man nach eigenen Angaben nur Schichtdicken bis zu etwa 20 µm. Allerdings muß der pH-Wert in engen Grenzen konstant gehalten werden. Bei pH-Werten unterhalb 3 löst sich die Platinschicht wieder ab.DE-PS 12 56 992 describes a galvanic platinum bath which consists of an aqueous solution of Platinum diamminodinitrite (P salt) and alkali metal salts of sulfamic acid exist and are operated at pH values from 6.5 to 8. Here, too, you get only layer thicknesses of up to about 20 µm. However, the pH must be kept constant within narrow limits. At pH values below 3, the platinum layer will come off again.

Nach der DE-AS 11 44 074 wird das P-Salz mit einem hohen Überschuß an Sulfamidsäure, NH2SO3H, umgesetzt, so daß man nach Verdünnen mit Wasser ein gebrauchsfertiges Bad erhält, das 6-20 g/l Platin und 20-100 g/l Sulfamidsäure (Amidoschwefelsäure)enthält. Jedoch ist dieser Elektrolyt nur so lange stabil, wie das Bad in Betrieb ist. Dicke Schichten können rißfrei nur mit matter Oberfläche erhalten werden.According to DE-AS 11 44 074, the P salt is reacted with a large excess of sulfamic acid, NH 2 SO 3 H, so that a diluted bath with 6-20 g / l platinum and 20 Contains -100 g / l sulfamic acid (amidosulfuric acid). However, this electrolyte is only stable as long as the bath is in operation. Thick layers can only be obtained without cracks with a matt surface.

Es war daher Aufgabe der vorliegenden Erfindung, ein galvanisches Platinbad insbesondere zur Abscheidung dicker Schichten zu entwickeln, das 5 bis 30 g/l Platin als Amminsulfamato-Komplex enthält und einen pH-Wert von weniger als 1 aufweist, mit dem auch Schichtdicken über 100 µm rißfrei, glatt und glänzend abgeschieden werden können und das auch bei Nichtbenutzung stabil ist.It was therefore an object of the present invention to develop a galvanic platinum bath, in particular for depositing thick layers, which contains 5 to 30 g / l of platinum as amine sulfamato complex and has a pH of less than 1, with which layer thicknesses of more than 100 μm are also possible can be deposited without cracks, smooth and shiny and that is stable even when not in use.

Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß der Elektrolyt höchstens 5 g/l freie Amidoschwefelsäure (Sulfamidsäure) und 20 bis 400 g/l einer starken Säure mit einem pH-Wert kleiner 1 enthält.This object is achieved in that the electrolyte contains at most 5 g / l of free amidosulfuric acid (sulfamic acid) and 20 to 400 g / l of a strong acid with a pH value less than 1.

Vorzugsweise wird als starke Säure Schwefelsäure, Methansulfonsäure oder Perchlorsäure eingesetzt. Daneben können auch andere Mineralsäuren, wie Fluorschwefelsäure oder Fluoroborsäure, Alkansulfonsäuren, wie Methandisulfonsäure, Ethansulfonsäure, Hydroxiethansulfonsäure und Homologe, oder perfluorierte Alkansulfonsäuren, wie Trifluormethansulfonsäure oder Pentafluorethansulfonsäure, und Perfluorcarbonsäuren, wie Trifluoressigsäure, eingesetzt werden.Sulfuric acid, methanesulfonic acid or perchloric acid is preferably used as the strong acid. In addition, other mineral acids, such as fluorosulfuric acid or fluoroboric acid, alkanesulfonic acids, such as methanedisulfonic acid, ethanesulfonic acid, hydroxyethanesulfonic acid and homologues, or perfluorinated alkanesulfonic acids, such as trifluoromethanesulfonic acid or pentafluoroethanesulfonic acid, and perfluorocarboxylic acids, such as trifluoroacetic acid, can also be used.

Außerdem ist es von Vorteil, wenn der Elektrolyt zusätzlich 0,01 bis 0,2 g/l eines Fluortensids als Netzmittel enthält.It is also advantageous if the electrolyte additionally contains 0.01 to 0.2 g / l of a fluorosurfactant as a wetting agent.

Bewährt hat es sich, wenn als Amminsulfamato-Komplex das Produkt aus der Umsetzung von 1 Mol P-Salz (Platindiamminodinitrito-Komplex) mit 4 bis 6 Mol Amidoschwefelsäure eingesetzt wird.It has proven useful if the product from the reaction of 1 mol of P salt (platinum diamminodinitrito complex) with 4 to 6 mol of amidosulfuric acid is used as the amine sulfamato complex.

Sehr gute Abscheideergebnisse erhält man, wenn das Platin-P-Salz mit Amidoschwefelsäure in äquivalenten Mengen umgesetzt wird und die resultierende Platinsulfamato-Komplexlösung einer wäßrigen Lösung einer starken Säure zugegeben wird, wobei die Säure z.B. Schwefelsäure, Methansulfonsäure oder Perchlorsäure sein kann. Dabei muß das Bad eine ausreichende Menge der starken Säure enthalten. Bewährt haben sich Mengen von 20 bis 400 g/l.Very good deposition results are obtained when the platinum P salt is reacted with amidosulfuric acid in equivalent amounts and the resulting platinum sulfamato complex solution is added to an aqueous solution of a strong acid, the acid e.g. Can be sulfuric acid, methanesulfonic acid or perchloric acid. The bath must contain a sufficient amount of the strong acid. Quantities of 20 to 400 g / l have proven effective.

Das Bad kann außerdem 0,01-0,2 g/l eines Fluortensids zur Unterdrückung von Sprühnebeln enthalten. Es wird bei Temperatur zwischen 60 und 90° C und bei Stromdichten von 1-4 A/dm2 betrieben.The bath may also contain 0.01-0.2 g / l of a fluorosurfactant to suppress spray. It is operated at a temperature between 60 and 90 ° C and at current densities of 1-4 A / dm 2 .

Die Platinamminsulfamato-Komplexlösung erwies sich in dem stark sauren Bad ohne freie Amidoschwefelsäure als überraschend stabil. Das Bad zeigte auch bei langen Elektrolysezeiten keinerlei Niederschlagsbildung. Bei der Abscheidung des Platins freiwerdendes Sulfamat wird rasch hydrolysiert und reichert sich nicht im Elektrolyten an.The platinum amine sulfamato complex solution proved to be surprisingly stable in the strongly acidic bath without free amidosulfuric acid. The bath showed no precipitation even with long electrolysis times. When the platinum is released, sulfamate is rapidly hydrolyzed and does not accumulate in the electrolyte.

Die aus diesen Bädern abgeschiedenen Platinüberzüge sind rißfrei, glänzend und duktil auch bei Schichtdicken über 100 µm.The platinum coatings deposited from these baths are crack-free, shiny and ductile even with layer thicknesses over 100 µm.

Folgendes Beispiel zeigt die Vorteile des erfindungsgemäßen Bades:
Ein galvanisches Platinbad wird wie folgt bereitet:
80 ml Schwefelsäure (97 %) werden in ca. 600 ml Wasser verdünnt. Dieser Lösung werden 16 g Platin in Form der Platinamminsulfamato-Komplexlösung und 0,1 g eines Fluortensids zugegeben. Nach Auffüllen mit Wasser erhält man 1 l fertiges Bad. Bei einer Badtemperatur von 80° C und einer Stromdichte von 2 A/dm2 wird ein Teil aus Silber bei rotierender Bewegung beschichtet. Nach ca. 13 Stunden hat sich eine ca. 120 µm dicke, glänzende Platinschicht gleichmäßig abgeschieden. Nach Ablösen des Silbers mit Salpetersäure, verdünnt 1:1, erhält man eine stabile, rißfreie Platinfolie.
The following example shows the advantages of the bath according to the invention:
A galvanic platinum bath is prepared as follows:
80 ml of sulfuric acid (97%) are diluted in approx. 600 ml of water. This solution contains 16 g of platinum in the form of Platinum amine sulfamato complex solution and 0.1 g of a fluorosurfactant added. After filling with water, 1 l of the finished bath is obtained. At a bath temperature of 80 ° C and a current density of 2 A / dm 2 , a part made of silver is coated while rotating. After approx. 13 hours, an approx. 120 µm thick, shiny platinum layer has deposited evenly. After removing the silver with nitric acid, diluted 1: 1, a stable, crack-free platinum foil is obtained.

Claims (4)

Galvanisches Platinbad, insbesondere zur Abscheidung dicker Schichten, das 5 bis 30 g/l Platin als Amminsulfamato-Komplex enthält und einen pH-Wert von weniger als 1 aufweist,
dadurch gekennzeichnet,
daß der Elektrolyt höchstens 5 g/l freie Amidoschwefelsäure und 20 bis 400 g/l einer starken Säure mit einem pH-Wert kleiner 1 enthält.
Galvanic platinum bath, in particular for the deposition of thick layers, which contains 5 to 30 g / l platinum as amine sulfamato complex and has a pH of less than 1,
characterized,
that the electrolyte contains at most 5 g / l of free amidosulfuric acid and 20 to 400 g / l of a strong acid with a pH of less than 1.
Galvanisches Platinbad gemäß Anspruch 1,
dadurch gekennzeichnet,
daß als starke Säure Schwefelsäure, Methansulfonsäure oder Perchlorsäure eingesetzt wird.
Galvanic platinum bath according to claim 1,
characterized,
that sulfuric acid, methanesulfonic acid or perchloric acid is used as the strong acid.
Galvanisches Platinbad gemäß Anspruch 1 oder 2,
dadurch gekennzeichnet,
daß es 0,01 bis 0,2 g/l eines Fluortensids als Netzmittel enthält.
Galvanic platinum bath according to claim 1 or 2,
characterized,
that it contains 0.01 to 0.2 g / l of a fluorosurfactant as a wetting agent.
Galvanisches Platinbad gemäß Anspruch 1,
dadurch gekennzeichnet,
daß als Ammin-sulfamato-Komplex das Produkt aus der Umsetzung von 1 Mol Diamminodinitritoplatin(II) mit 4 bis 6 Mol Amidoschwefelsäure eingesetzt wird.
Galvanic platinum bath according to claim 1,
characterized,
that the product from the reaction of 1 mole of diamminodinitritoplatinum (II) with 4 to 6 moles of amidosulfuric acid is used as the amine-sulfamato complex.
EP96102799A 1995-04-15 1996-02-24 Platinum electroplating bath Expired - Lifetime EP0737760B1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19514253 1995-04-15
DE19514253 1995-04-15
DE19547900 1995-12-21
DE19547900A DE19547900C2 (en) 1995-04-15 1995-12-21 Galvanic platinum bath

Publications (2)

Publication Number Publication Date
EP0737760A1 true EP0737760A1 (en) 1996-10-16
EP0737760B1 EP0737760B1 (en) 2000-04-19

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US (1) US5620583A (en)
EP (1) EP0737760B1 (en)
JP (1) JPH08319595A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022129461A1 (en) 2020-12-18 2022-06-23 Umicore Galvanotechnik Gmbh Stabilization of the deposition rate of platinum electrolytes
DE102021107826A1 (en) 2021-03-29 2022-09-29 Umicore Galvanotechnik Gmbh platinum electrolyte

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US6294425B1 (en) 1999-10-14 2001-09-25 Samsung Electronics Co., Ltd. Methods of forming integrated circuit capacitors by electroplating electrodes from seed layers
US20020000380A1 (en) * 1999-10-28 2002-01-03 Lyndon W. Graham Method, chemistry, and apparatus for noble metal electroplating on a microelectronic workpiece
KR100331570B1 (en) 2000-06-13 2002-04-06 윤종용 Method for manufacturing capacitor of semiconductor memory device using electroplating method
US7150820B2 (en) * 2003-09-22 2006-12-19 Semitool, Inc. Thiourea- and cyanide-free bath and process for electrolytic etching of gold
US20050230262A1 (en) * 2004-04-20 2005-10-20 Semitool, Inc. Electrochemical methods for the formation of protective features on metallized features
FR2974582A1 (en) * 2011-04-27 2012-11-02 Commissariat Energie Atomique PROCESS FOR GROWING METALLIC PARTICLES BY ELECTRODEPOSITION WITH IN SITU INHIBITION
GB201200482D0 (en) * 2012-01-12 2012-02-22 Johnson Matthey Plc Improvements in coating technology
US10612149B1 (en) 2019-09-05 2020-04-07 Chow Sang Sang Jewellery Company Limited Platinum electrodeposition bath and uses thereof
TWI784601B (en) 2021-01-08 2022-11-21 日商Eeja股份有限公司 Platinum electroplating baths and platinum-plated products

Citations (2)

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EP0358375A1 (en) * 1988-09-07 1990-03-14 Johnson Matthey Public Limited Company Platinum or platinum alloy plating bath
JPH04297592A (en) * 1991-03-25 1992-10-21 Tanaka Kikinzoku Kogyo Kk Platinum electroplating bath

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL123540C (en) * 1958-08-06

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0358375A1 (en) * 1988-09-07 1990-03-14 Johnson Matthey Public Limited Company Platinum or platinum alloy plating bath
JPH04297592A (en) * 1991-03-25 1992-10-21 Tanaka Kikinzoku Kogyo Kk Platinum electroplating bath

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 17, no. 113 (C - )<1033> 9 March 1993 (1993-03-09) *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022129461A1 (en) 2020-12-18 2022-06-23 Umicore Galvanotechnik Gmbh Stabilization of the deposition rate of platinum electrolytes
DE102020007789A1 (en) 2020-12-18 2022-06-23 Umicore Galvanotechnik Gmbh Stabilization of the deposition rate of platinum electrolytes
DE102021107826A1 (en) 2021-03-29 2022-09-29 Umicore Galvanotechnik Gmbh platinum electrolyte
WO2022207539A1 (en) 2021-03-29 2022-10-06 Umicore Galvanotechnik Gmbh Platinum electrolyte

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US5620583A (en) 1997-04-15
JPH08319595A (en) 1996-12-03
EP0737760B1 (en) 2000-04-19

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