EP2283170A1 - Bains d'électrolyte au pd et au pd-ni - Google Patents

Bains d'électrolyte au pd et au pd-ni

Info

Publication number
EP2283170A1
EP2283170A1 EP08758401A EP08758401A EP2283170A1 EP 2283170 A1 EP2283170 A1 EP 2283170A1 EP 08758401 A EP08758401 A EP 08758401A EP 08758401 A EP08758401 A EP 08758401A EP 2283170 A1 EP2283170 A1 EP 2283170A1
Authority
EP
European Patent Office
Prior art keywords
electrolyte
palladium
electrolyte according
nickel
group
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
EP08758401A
Other languages
German (de)
English (en)
Other versions
EP2283170B1 (fr
Inventor
Sascha Berger
Frank Oberst
Franz Simon
Uwe Manz
Bernd Weyhmueller
Klaus Bronder
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.)
Umicore Galvanotechnik GmbH
Original Assignee
Umicore Galvanotechnik GmbH
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 Umicore Galvanotechnik GmbH filed Critical Umicore Galvanotechnik GmbH
Priority to PL08758401T priority Critical patent/PL2283170T3/pl
Publication of EP2283170A1 publication Critical patent/EP2283170A1/fr
Application granted granted Critical
Publication of EP2283170B1 publication Critical patent/EP2283170B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
    • C25D3/52—Electroplating: Baths therefor from solutions of platinum group metals characterised by the organic bath constituents used
    • 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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/567—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of platinum group metals

Definitions

  • the present invention relates to an electrolyte for the electrodeposition of palladium or palladium alloys on metallic or conductive substrates.
  • this is a Pd electrolyte containing optionally further metals and an organic oligoamine as a complexing agent, with the alloy coatings with e.g. 80% Pd for technical and decorative applications can be deposited.
  • the invention is directed to a corresponding galvanotechnisches method using this electrolyte and special, advantageously usable for this process palladium salts.
  • the electrodeposition of palladium or palladium alloys on metallic substrates has a variety of decorative and technical applications.
  • Galvanically deposited pure palladium and palladium-nickel layers, if appropriate each with gold flash, are recognized materials, e.g. for low-current contacts or plug contacts (for example on printed circuit boards) and can be considered as a replacement for hard gold [Galvanotechnik 5 (2002), 121 Off, Simon u. Yasumura: "Galvanic Palladium Layers for Technical Applications in Electronics”].
  • palladium deposits with a very small layer thickness on so-called lead frames in semiconductor production can replace the silver used in the bond area [Galvanotechnik 6 (2002), 1473ff, Simon et al. Yasumura: "Galvanic Palladium Layers for Technical Applications in Electronics”].
  • Patent DE 4428966 (US Pat. No. 5,415,685) describes a palladium bath in which, in addition to a palladium compound (namely palladium diaminodinitrite) and various ammonium salts (sulfate, citrate and phosphate), a combination of gloss additives is also mentioned.
  • the described ammoniacal process operates in a pH range between 5 and 12.
  • the claimed brighteners are a combination of a sulfonic acid and an aromatic N-heterocycle. Specifically named are, inter alia, o-formylbenzenesulfonic acid and 1- (3-sulfopropyl) -2-vinylpyridinium betaine.
  • pyridines mentioned by name are 1- (3-sulfopropylpyridinium betaine and 1- (2-hydroxy-3-sulfopropylpyridinium betaine). The latter two substances have, according to the authors, a negative effect on the gloss of the resulting coatings.
  • a process according to US6743346 also employs ethylenediamine as a complexing agent and incorporates the palladium in the form of the solid compound of palladium sulfate and ethylenediamine.
  • the salt contains 31 to 41% palladium (mole ratios [SO 4 ]: [Pd] between 0.9 and 1.15 and [ethylene diamine]: [Pd] between 0.8 and 1.2). It is insoluble in water but dissolves in the electrolyte with excess ethylenediamine (Plating & Surface Finishing, (2007) 4, pp. 26-35, St. Burling "Precious Metal Plating and the Environment").
  • As brighteners here are the substances 3- (3-pyridyl) acrylic acid or 3- ( It is mentioned that the brighteners based on sulfonates are not able to ensure the desired gloss, especially at current densities of 15 to 150 A / dm 2 , in galvanic electrolytes.
  • Object of the present invention was in the context of the cited prior art, the indication of a further electrolyte and working with this electrolyte process, which help overcome the disadvantages mentioned.
  • the specified electrolyte composition or the corresponding method should help to produce glossy surfaces even at high current densities and fast electrolysis processes, which would be particularly advantageous from an economic and ecological point of view.
  • aqueous electrolyte for the electrodeposition of palladium or a palladium alloy on a metallic or conductive substrate, which to be deposited, complexed with organic oligoamines metal ions in the form of their salts with oxide hydroxide, hydroxide, bicarbonate and / or carbonate as Having counterions and a brightener based on an inner salt of a quaternary ammonium and a sulfonic acid group, one arrives in a surprisingly simple manner and successfully to solve the problem.
  • the electrolyte according to the invention or by using the method according to the invention it is now possible to produce the desired shiny surfaces with qualitatively excellent results both at low and at high current densities.
  • the electrolyte composition according to the invention is in no way suggested by the prior art.
  • the electrolyte according to the invention makes it possible to deposit the palladium alone or in the form of an alloy associated with other metals.
  • Other metals that can be used in the art for this purpose in question. These may be e.g. Nickel, cobalt, iron, indium, gold, silver or tin or mixtures thereof.
  • the metal ions to be deposited are selected from the group consisting of nickel, cobalt, iron and mixtures thereof.
  • the electrolyte contains these metals in the form of their soluble salts.
  • Suitable salts are preferably those selected from the group of phosphates, carbonates, bicarbonates, hydroxides, oxides, sulfates, sulfamates, alkanesulfonates, pyrophosphates, phosphonates, nitrates, carboxylic acid salts and mixtures thereof.
  • the person skilled in the art selects the concentrations of the metals to be used in the electrolyte on the basis of his general technical knowledge. It has been found that advantageous results can be obtained when palladium is used in concentrations of 1-100 g / L, preferably 2-70 g / L, and more preferably 4-50 g / L and most preferably 5-25 g / L is present based on the electrolyte.
  • the further metal ions to be deposited can be present in concentrations of ⁇ 50 g / L based on the electrolyte. Preferably, the concentration of these ions in the electrolyte ⁇ 40 g / L, more preferably ⁇ 30 g / L based on the electrolyte.
  • a uniform deposition of the metal ions under the conditions according to the invention is advantageous, inter alia, if they are complexed.
  • Suitable oligonucleotides for these complexes have proven to be organic oligoamines.
  • Advantageous is the use of polydentate, in particular ligands based on di-, tri- or tetraamines. Particularly preferred are those having 2 to 11 carbon atoms.
  • Very particular preference is given to the use of ligands selected from the group consisting of ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,2-propylenediamine, trimethylenetetramine, hexamethylenetetramine.
  • EDA ethylene diamine
  • oligoamines used in the estimation of the amount. In the estimation of the amount, he will orientate himself by the fact that a sufficient amount must be present in order to obtain as even as possible a deposition of the palladium or of the palladium alloy. On the other hand, at least economic considerations limit the use of large quantities of oligoamines.
  • An amount of 0.1-5 mol / L of oligoamines in the electrolyte is advantageous. More preferably, the concentration is in the range between 0.3-3 mol / L. Most preferably, the concentration of oligoamines at 0.5 - 2 mol / L electrolyte.
  • the pH of the electrolyte according to the invention can be adjusted according to the skilled person for the particular application in the acidic to neutral range.
  • a further preferred range is from pH 3.5 to pH 6.5, more preferably from pH 4 to pH 6, and most preferably around pH 5 to pH 5 ; 5.
  • the electrolyte according to the invention has brighteners based on an internal salt of a quaternary ammonium and an acid group.
  • a quaternary ammonium compound is preferably one in which the positively charged nitrogen atom is part of an aromatic ring system.
  • Those skilled in the art are particularly suitable as such molecular constituents, which relate to a mononuclear or polynuclear aromatic systems, such as pyridinium, pyrimidinium, pyrazinium, pyrrolinium, imidazolinium, thiazolinium, indolinium, carbazolinium or such substituted systems in consideration.
  • pyridinium- or alkyl- or alkenyl-substituted pyridinium derivatives used.
  • a brightener having as a molecular constituent a quaternary ammonium compound based on a pyridinium derivative.
  • the brightener contains an acid group, so that in the present case the brightener is an internal salt or a betaine.
  • the term "acid group” refers to a group which, under the given conditions, is present predominantly in the deprotonated form in the electrolyte.
  • the acid group may be derived from those selected from the group consisting of phosphoric acid, phosphonic acid, sulfuric acid, sulfonic acid, carboxylic acid. Particularly preferred is the sulfonic acid as part of the brightener.
  • the acid group and the quaternary ammonium moiety of the brightener may be linked by (CrCsJ-alkylene-, (d-C ⁇ J-alkenylene-, (C 6 -C 18 ) -arylene, which may optionally be substituted, being highly preferred compounds in this
  • those selected from the group consisting of 1- (3-sulfopropyl) -2-vinylpyridinium betaine), 1- (3-sulfopropylpyridinium betaine and 1- (2-hydroxy-3-sulfopropylpyridinium betaine have proven.
  • the brightener can be used in quantities which are obvious to a person skilled in the art.
  • An upper limit is the amount of brightener, in which the cost of its use is no longer justified by the effect achieved.
  • the use of the brightener is thus advantageous in amounts of from 1 to 10000 mg / L of electrolyte.
  • the brightener is used in a concentration of 5 to 5000 mg / L of electrolyte, most preferably in an amount of 10 to 1000 mg / L of electrolyte.
  • the electrolyte according to the invention may contain further constituents which have a positive influence with regard to the bath stability, the deposition behavior of the metals, the quality of the deposited material and the electrolysis conditions.
  • those skilled in the art in particular means for reducing the internal stresses of the coating, wetting agents, conductive salts, other brighteners and / or buffer substances, etc. into consideration.
  • additives for reducing the surface tension of the electrolyte wetting agents can be selected from the following groups consisting of anionic wetting agents such as sodium lauryl sulfate, dodecylbenzenesulfonate sodium salt, sodium dioctylsulfosuccinate, nonionic wetting agents such as polyethylene glycol Fatty acid esters and / or cationic wetting agents such as cetyltrimethylammonium be used.
  • anionic wetting agents such as sodium lauryl sulfate, dodecylbenzenesulfonate sodium salt, sodium dioctylsulfosuccinate
  • nonionic wetting agents such as polyethylene glycol Fatty acid esters and / or cationic wetting agents such as cetyltrimethylammonium be used.
  • Conducting salts selected from the group consisting of potassium sulfate or sodium sulfate, phosphate, nitrate, alkanesulfonate, sulfamate and mixtures thereof can advantageously be used to improve the conductivity and throwing power of the electrolyte.
  • buffer substances are those selected from the group consisting of boric acid or phosphates or a carboxylic acid and / or salts thereof, such as e.g. Acetic acid, citric acid, tartaric acid, oxalic acid, succinic acid, malic acid, lactic acid, phthalic acid.
  • brightener additives may advantageously those selected from the group consisting of N, N-diethyl-2-propyn-1-amine, 1,1-dimethyl-2-propynyl-1-amine, 2-butyne-1, 4-diol, 2-butyne-1,4-diol ethoxylate, 2-butyne-1,4-diol propoxylate, 3-hexyne-2,5-diol and sulfopropylated 2-butyne-1,4-diol or one of their salts.
  • Other base gloss agents may be allylsulfonic acid and / or vinylsulfonic acid and / or
  • Propargylsulfonklare or their alkali metal salts in amounts of 0.01 to 10 g / L electrolyte.
  • those selected from the group consisting of iminodisuccinic acid and / or sulfamic acid and / or sodium saccharinate may be advantageously used.
  • no further metal salts with inorganic anions except sulfate or nitrate, bicarbonate or carbonate ions or oxide, hydroxide or mixtures thereof are added to the electrolyte.
  • Such an approach in turn has a positive effect on the service life of the electrolyte.
  • Particularly advantageous is the embodiment in which only those deposition metal salts are used whose anions consist of bicarbonate or carbonate ions or oxide, hydroxide or mixtures thereof.
  • the present invention also provides a process for the electrodeposition of palladium or a palladium alloy on a metallic or conductive substrate, wherein an electrolyte according to the invention is used.
  • the palladium or palladium alloy may be electrodeposited on substrates well known to those skilled in the art for this purpose.
  • the metallic or electrically conductive substrates are selected from the group consisting of nickel, nickel alloys, gold, silver, copper and copper alloys, iron, iron alloys. Particularly preferred is nickel or copper or
  • the temperature in the electrolytic deposition can be chosen arbitrarily by the expert.
  • the temperature is set at which a corresponding desired deposition can take place. This is the case at temperatures from 2O 0 C to 80 0 C.
  • a temperature of 30 0 C to 70 0 C and most preferably from 40 ° C to 60 ° C is set.
  • the current density to be set can be selected by the person skilled in the art according to the underlying electrolysis arrangement during the electrolysis according to the invention.
  • the current densities are preferably between 0.1 and 150 A / dm 2 . Particularly preferred are 0.1-10.0 A / dm 2 for drum and rack applications and 5.0-100 A / dm 2 for high speed applications. Most preferably, 5.0-70 A / dm 2 is set for high-speed applications, and 0.2-5 A / dm 2 is most preferred in drum and rack applications.
  • the inventive method is advantageously carried out so that the deposition is carried out using non-soluble anodes.
  • non-soluble anodes particularly preferred is the use of insoluble anodes of platinized titanium or mixed oxide anodes. These are most preferably non-soluble anodes of platinized titanium or iridium / ruthenium / tantalum oxide coated titanium or niobium or tantalum.
  • Anodes made of graphite or of durable stainless steel are also possible.
  • the subject matter of the present invention is likewise a special palladium salt which can advantageously be used and adapted for the process according to the invention.
  • These are a palladium complex compounds consisting of a divalent palladium cation, one or more di-, tri- or tetradentate organic amine ligands and carbonate or two bicarbonate or hydroxyl anions or a mixture thereof.
  • the advantage here is the use of multidentate ligands based on di-, tri or tetraamines. Particularly preferred are those having 2 to 11 carbon atoms.
  • ligands selected from the group consisting of ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,2-propylenediamine, trimethylenetetramine, hexamethylenetetramine.
  • EDA ethylene diamine
  • the reaction temperature is preferably between 20 and 95 0 C, more preferably between 40 and 90 0 C, most preferably between 60 and 80 0 C.
  • an electrolyte of the invention described herein with, for example, 20 g / l of palladium as bis (ethylenediamino) -palladium (II) hydrogen carbonate, 16 g / l of nickel as nickel (II) sulfate and 50 g / l of ethylenediamine enable the brighteners 1- (3 - Sulfopropylpyridiniumbetain or 1- (2-hydroxy-3-sulfopropylpyridiniumbetain in amounts of 50 to 500 mg / l, especially in the low current density range the
  • Ammonia and chloride are also avoided with the new palladium-nickel electrolyte based on ethylenediamine, which significantly reduces the risk potential and the unpleasant odor for humans and plant corrosion.
  • the disadvantages of the previous, ammonium and chloride-free ethylene-diamine based processes are avoided.
  • the use of carbonate or bicarbonate as counter ions to palladium and nickel allows an extension of the service life.
  • the anions used are not stable in the applied pH range between, for example, 3 and 5.5 and decompose immediately upon addition of the metal salt to carbon dioxide and hydroxide. The volatile CO 2 escapes from the electrolyte and thus does not contribute to increasing the bath density.
  • the indicated constituents of the electrolyte are dissolved in 4 L of deionized water. Subsequently, the palladium or the palladium alloy is deposited on a brass sheet under the given electrolysis conditions.
  • An electrolyte for depositing PdNi layers with 80% by weight of palladium may be e.g. have the following composition:
  • Electrolyte for high-speed deposition 20 g / l Pd as bis (ethylenediamino) palladium (II) bicarbonate
  • Substrate Copper or copper alloy, possibly undepleted
  • the resulting coatings (2 microns) are homogeneously shiny, bright, ductile, crack-free in the current density range mentioned and have a relatively constant Pd content of 80 to 83%.
  • Substrate copper or copper alloy, possibly nickel-plated anodes: Pt / Ti
  • the resulting coatings (2 microns) are homogeneously high gloss in the current density range mentioned, brilliant-bright, very ductile, crack-free and have a relatively constant Pd content of 80 to 83%.
  • Tetraamminepalladium (II) bicarbonate (product # 45082) from Alfa Aesar Ethylene diamine 99% for synthesis (e.g., Merck # 800947)

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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)
  • Chemically Coating (AREA)
EP08758401A 2008-05-07 2008-05-07 Bains d'électrolyte au pd et au pd-ni Active EP2283170B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL08758401T PL2283170T3 (pl) 2008-05-07 2008-05-07 Kąpiele elektrolitowe PD i PD-NI

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2008/003667 WO2009135505A1 (fr) 2008-05-07 2008-05-07 Bains d'électrolyte au pd et au pd-ni

Publications (2)

Publication Number Publication Date
EP2283170A1 true EP2283170A1 (fr) 2011-02-16
EP2283170B1 EP2283170B1 (fr) 2012-04-25

Family

ID=40193655

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08758401A Active EP2283170B1 (fr) 2008-05-07 2008-05-07 Bains d'électrolyte au pd et au pd-ni

Country Status (10)

Country Link
US (1) US8900436B2 (fr)
EP (1) EP2283170B1 (fr)
JP (1) JP5586587B2 (fr)
KR (1) KR101502804B1 (fr)
CN (1) CN102037162B (fr)
AT (1) ATE555235T1 (fr)
ES (1) ES2387055T3 (fr)
PL (1) PL2283170T3 (fr)
TW (1) TWI475134B (fr)
WO (1) WO2009135505A1 (fr)

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RU2469697C1 (ru) * 2011-05-23 2012-12-20 Открытое акционерное общество "Научно-производственный комплекс "Суперметалл" имени Е.И. Рытвина" Способ нанесения гальванического покрытия на съемные зубные протезы
US10263467B2 (en) * 2012-12-12 2019-04-16 Ls Cable & System Ltd. Antenna for wireless power, and dual mode antenna comprising same
CN106661735B (zh) * 2014-09-04 2019-12-10 日本高纯度化学株式会社 钯镀液和使用该钯镀液得到的钯覆膜
JP6189878B2 (ja) * 2015-01-14 2017-08-30 松田産業株式会社 パラジウム又はパラジウム合金めっき用シアン耐性付与剤、めっき液、めっき液へのシアン耐性付与方法
AT516876B1 (de) * 2015-03-09 2016-11-15 Ing W Garhöfer Ges M B H Abscheidung von dekorativen Palladium-Eisen-Legierungsbeschichtungen auf metallischen Substanzen
US20180053714A1 (en) * 2016-08-18 2018-02-22 Rohm And Haas Electronic Materials Llc Multi-layer electrical contact element
JP6663335B2 (ja) * 2016-10-07 2020-03-11 松田産業株式会社 パラジウム−ニッケル合金皮膜及びその製造方法
KR101867733B1 (ko) * 2016-12-22 2018-06-14 주식회사 포스코 철-니켈 합금 전해액, 표면조도가 우수한 철-니켈 합금 포일 및 이의 제조방법
CN107385481A (zh) * 2017-07-26 2017-11-24 苏州鑫旷新材料科技有限公司 一种无氰电镀金液
EP3456870A1 (fr) * 2017-09-13 2019-03-20 ATOTECH Deutschland GmbH Bain et procédé de remplissage d'une tranchée ou d'un accès d'interconnexion verticale d'une pièce à usiner, de nickel ou d'un alliage de nickel
CN108864200B (zh) * 2018-08-06 2020-12-11 金川集团股份有限公司 电镀用硫酸乙二胺钯的一步制备方法
DE102018133244A1 (de) 2018-12-20 2020-06-25 Umicore Galvanotechnik Gmbh Nickel-Amin-Komplex mit reduzierter Tendenz zur Bildung schädlicher Abbauprodukte
CN110144729B (zh) * 2019-06-14 2020-07-07 中国科学院长春应用化学研究所 一种导电金包覆聚酰亚胺纤维及其制备方法
JP7282136B2 (ja) * 2021-02-12 2023-05-26 松田産業株式会社 パラジウムめっき液及びパラジウムめっき補充液

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Also Published As

Publication number Publication date
TWI475134B (zh) 2015-03-01
JP5586587B2 (ja) 2014-09-10
CN102037162B (zh) 2013-03-27
TW201006967A (en) 2010-02-16
US20110168566A1 (en) 2011-07-14
EP2283170B1 (fr) 2012-04-25
CN102037162A (zh) 2011-04-27
JP2011520036A (ja) 2011-07-14
KR101502804B1 (ko) 2015-03-16
ATE555235T1 (de) 2012-05-15
US8900436B2 (en) 2014-12-02
PL2283170T3 (pl) 2012-09-28
ES2387055T3 (es) 2012-09-12
KR20110003519A (ko) 2011-01-12
WO2009135505A1 (fr) 2009-11-12

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