EP2737107B1 - Composition de bain de nickelage autocatalytique - Google Patents

Composition de bain de nickelage autocatalytique Download PDF

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Publication number
EP2737107B1
EP2737107B1 EP12743909.9A EP12743909A EP2737107B1 EP 2737107 B1 EP2737107 B1 EP 2737107B1 EP 12743909 A EP12743909 A EP 12743909A EP 2737107 B1 EP2737107 B1 EP 2737107B1
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EP
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Prior art keywords
plating bath
nickel
ranges
concentration
hypophosphite
Prior art date
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EP12743909.9A
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German (de)
English (en)
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EP2737107A1 (fr
Inventor
Boris Alexander Janssen
Holger BERA
Sebastian Weißbrod
Britta Schafsteller
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Atotech Deutschland GmbH and Co KG
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Atotech Deutschland GmbH and Co KG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites

Definitions

  • the present invention relates to an aqueous plating bath composition for the electroless deposition of nickel phosphorous alloys.
  • Electroless plating of nickel-phosphorous alloys is used in various industries.
  • the deposits derived are used e.g. as wear resistant coatings and barrier layers.
  • Such plating bath compositions generally comprise a source of nickel ions, a hypophosphite compound as the reducing agent, at least one complexing agent and at least one stabilizing agent.
  • the at least one stabilizing agent present is required in order to provide a sufficient bath lifetime, a reasonable deposition rate and to control the phosphorous content in the as deposited nickel phosphorous alloy.
  • plating baths for deposition of nickel-phosphorous alloys known in the art comprise more than one stabilizing agent.
  • Common stabilizing agents are selected from heavy metal ions such as cadmium, thallium, bismuth, lead and antimony ions, inorganic ions such as SCN- and various organic compounds such as thiourea.
  • the patent document US 2,830,014 discloses plating bath compositions for electroplating of nickel which comprise thioalkane sulfonic acids or salts thereof such as mercaptopropane-1-sodium sulfonate as brightening and ductility-improving agents.
  • the patent application US 2005/0013928 A1 discloses an electroless plating pre-treatment solution which comprises 3-mercaptopropanesulfonic acid.
  • the pre-treatment solution reduces the incubation time (time from the start of the supply of an electroless plating solution to the start of the plating reaction) of nickel plating from an electroless plating bath on a copper surface.
  • the patent application US 2006/024043 A1 discloses an alkaline aqueous plating bath for deposition of nickel phosphorous alloys which optionally comprises further additives such as thiourea and/or 3-mercapto-1-propane sulfonic acid. Such plating bath compositions are not acceptable for industrial applications (see Examples 2 to 5). Furthermore, thiourea is a carcinogenic substance.
  • CH620710 discloses an acidic electroless nickel plating bath comprising hypophosphite, complexing agent and a sulfur containing stabilising agent, namely thiourea, whereby a deposition of a nickel phosphorous alloy having a phosphorous concentration in the range between 7 and 10 wt.% is given.
  • an aqueous plating bath composition according to claim 1 for electroless plating of a nickel phosphorous alloy comprising
  • a nickel phosphorous alloy having a phosphorous content in the range of 5 to 12 wt.-% of phosphorous is derived by electroless plating.
  • the aqueous plating bath composition according to the present invention comprises a water soluble source of nickel ions such as nickel sulfate, a reducing agent such as sodium hypophosphite, at least one complexing agent and a stabilizing agent selected from compounds according to formulae (1) and (2).
  • the concentration of nickel ions ranges from 1 to 18 g/l, more preferably from 3 to 9 g/l.
  • the reducing agent is selected from hypophosphite compounds such as hypophosphorous acid or a bath soluble salt thereof such as sodium hypophosphite, potassium hypophosphite and ammonium hypophosphite.
  • the amount of the reducing agent employed in the plating bath ranges from 2 to 60 g/l, more preferably from 12 to 50 g/l and most preferably from 20 to 45 g/l. As a conventional practice the reducing agent is replenished during the reaction.
  • the complexing agents are employed in amounts of 1 to 200 g/l, more preferably from 15 to 75 g/l.
  • carboxylic acids, polyamines or mixtures thereof are selected as complexing agents.
  • Useful carboxylic acids include mono-, di-, tri- and tetra-carboxylic acids.
  • the carboxylic acids may be substituted with various substituent moieties such as hydroxy or amino groups and the acids may be introduced into the plating solutions as their sodium, potassium or ammonium salts.
  • Some complexing agents such as acetic acid, for example, may also act as a buffering agent, and the appropriate concentration of such additive components can be optimised for any plating solution in consideration of their dual functionality.
  • carboxylic acids which are useful as the complexing agents include: monocarboxylic acids such as acetic acid, hydroxyacetic acid, aminoacetic acid, 2-amino propanoic acid, 2-hydroxy propanoic acid, lactic acid; dicarboxylic acids such as succinic acid, amino succinic acid, hydroxy succinic acid, propanedioic acid, hydroxybutanedioic acid, tartaric acid, malic acid; tricarboxylic acids such as 2-hydroxy-1,2,3 propane tricarboxylic acid; and tetra-carboxylic acids such as ethylene diamine tetra acetic acid (EDTA).
  • monocarboxylic acids such as acetic acid, hydroxyacetic acid, aminoacetic acid, 2-amino propanoic acid, 2-hydroxy propanoic acid, lactic acid
  • dicarboxylic acids such as succinic acid, amino succinic acid, hydroxy succinic acid, propanedioic acid, hydroxybutaned
  • the most preferred complexing agents are selected from the group consisting of mono-carboxylic acids and di-carboxylic acids.
  • mixtures of two or more of the above complexing agents are utilized.
  • the stabilizing agent is selected from compounds according to formulae (1) and (2): R 1 S-(CH 2 ) n -SO 3 R 2 (1) R 3 SO 3 -(CH 2 ) m -S-S-(CH 2 ) m -SO 3 R 3 (2) wherein
  • R 1 is selected from the group consisting of hydrogen, sodium and potassium.
  • n ranges from 2 to 4.
  • R 2 is selected from the group consisting of hydrogen, sodium and potassium.
  • R 3 is selected from the group consisting of hydrogen, sodium and potassium.
  • m ranges from 2 to 4.
  • the concentration of the stabilizing agent according to formulae (1) and (2) in the plating bath composition ranges from 1 to 100 ppm, more preferably from 2 to 50 ppm and most preferably from 3 to 30 ppm.
  • the pH may be periodically or continuously adjusted by adding bath-soluble and bath-compatible alkaline substances such as sodium, potassium or ammonium hydroxides, carbonates and bicarbonates.
  • bath-soluble and bath-compatible alkaline substances such as sodium, potassium or ammonium hydroxides, carbonates and bicarbonates.
  • the stability of the operating pH of the plating solutions can be improved by the addition of various buffer compounds such as acetic acid, propionic acid, boric acid, or the like, in amounts of up to 30 g/l, more preferably from 2 to 10 g/l.
  • the pH value of the aqueous plating bath according to the present invention preferably ranges from 3.5 to 6.5, more preferably from 4 to 6.
  • nickel plating solutions such as buffers and wetting agents. These materials are known in the art.
  • the nickel plating solutions optionally may employ one or more wetting agents of any of the various types heretofore known which are soluble and compatible with the other bath constituents.
  • wetting agents prevents or hinders pitting of the nickel phosphorous alloy deposit, and the wetting agents can be employed in amounts up to about 1 g/l.
  • the substrate to be plated is contacted with the plating bath at a temperature of at least 40°C up to 95 °C.
  • the electroless nickel plating baths according to the present invention are employed, in one embodiment, at a temperature of from 70°C to 95°C, and more often, at a temperature of from 80°C to 90°C.
  • the duration of contact of the electroless nickel plating bath with the substrate being plated is a function which is dependent on the desired thickness of the nickel phosphorus alloy.
  • a contact time can range from 1 to 30 min.
  • the substrate to be coated with a nickel phosphorous alloy can be contacted with the plating bath according to the present invention by dipping the substrate into the plating bath or by spraying the plating bath onto the substrate.
  • mild agitation may be employed. Agitation may be a mild air agitation, mechanical agitation, bath circulation by pumping, rotation of a barrel plating, etc.
  • the plating solution may also be subjected to a periodic or continuous filtration treatment to reduce the level of contaminants therein. Replenishment of the constituents of the bath may also be performed, in some embodiments, on a periodic or continuous basis to maintain the concentration of constituents, and in particular, the concentration of nickel ions and hypophosphite ions, as well as the pH level within the desired limits.
  • the phosphorous concentration in the deposited nickel phosphorous alloys increases from 7.0 wt.-% at 1 MTO to 8.3 wt.-% at 3 MTO.
  • the plating rate of this plating bath is 0 ⁇ m/h.
  • the plating rate of this plating bath is 0 ⁇ m/h.
  • the plating rate of this plating bath is 0 ⁇ m/h.
  • the plating rate of this plating bath is 0 ⁇ m/h.
  • the stabilizing agent according to the present invention shows the desired properties in respect to the stable phosphorous concentration in the deposited nickel phosphorous alloy layers when using the plating bath. Furthermore, the plating rate is sufficient for industrial application.

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

Claims (8)

  1. Composition de bain aqueux de placage pour le dépôt autocatalytique d'un alliage de nickel-phosphore, le bain de placage comprenant
    (i) une source hydrosoluble d'ions nickel,
    (ii) un composé hypophosphite,
    (iii) au moins un agent complexant choisi dans le groupe comprenant les acides carboxyliques, les polyamines et les mélanges de ceux-ci et
    (iv) un agent stabilisant choisi dans le groupe constitué des composés répondant aux formules (1) et (2) :

            R1S-(CH2)n-SO3R2     (1)

            R3SO3-(CH2)m-S-S-(CH2)m-SO3R3     (2)

    dans lesquelles
    R1, R2 et R3 sont indépendamment choisis dans le groupe constitué par l'atome d'hydrogène, le groupe méthyle, le groupe éthyle, le groupe propyle, le groupe butyle, l'ion lithium, l'ion sodium, l'ion potassium et l'ion ammonium,
    n va de 1 à 6 et
    m va de 1 à 6
    et ayant une valeur de pH dans la plage de 3,5 à 6,5, dans laquelle la concentration de l'agent stabilisant répondant aux formules (1) et (2) va de 1 à 100 ppm.
  2. Bain aqueux de placage selon la revendication 1 dans lequel la concentration d'ions nickel va de 1 à
  3. Composition de bain aqueux de placage selon l'une quelconque des revendications précédentes dans laquelle le composé hypophosphite est choisi dans le groupe comprenant l'acide phosphoreux, l'hypophosphite de sodium, l'hypophosphite de potassium et l'hypophosphite d'ammonium.
  4. Bain aqueux de placage selon l'une quelconque des revendications précédentes dans lequel la concentration du composé hypophosphite va de 2 à 60 g/l.
  5. Bain aqueux de placage selon l'une quelconque des revendications précédentes dans lequel la concentration de l'au moins un agent complexant va de 1 à 200 g/l.
  6. Bain aqueux de placage selon l'une quelconque des revendications précédentes dans lequel la composition de bain de placage est exempte d'ions de métaux lourds choisis parmi le cadmium, le thallium, le plomb et l'antimoine.
  7. Bain aqueux de placage selon l'une quelconque des revendications précédentes ayant une valeur de pH dans la plage de 4 à 6.
  8. Procédé pour le dépôt d'un alliage de nickel-phosphore ayant une concentration en phosphore dans la plage de 5 à 12 % en poids, le procédé comprenant les étapes consistant à
    (i) fournir un substrat et
    (ii) mettre en contact ledit substrat avec un bain aqueux de placage selon les revendications 1 à 7.
EP12743909.9A 2011-07-26 2012-07-04 Composition de bain de nickelage autocatalytique Active EP2737107B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP12743909.9A EP2737107B1 (fr) 2011-07-26 2012-07-04 Composition de bain de nickelage autocatalytique

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP11175295A EP2551375A1 (fr) 2011-07-26 2011-07-26 Composition de bain pour placage autocatalytique de nickel
EP12743909.9A EP2737107B1 (fr) 2011-07-26 2012-07-04 Composition de bain de nickelage autocatalytique
PCT/EP2012/062967 WO2013013941A1 (fr) 2011-07-26 2012-07-04 Composition de bain de nickelage autocatalytique

Publications (2)

Publication Number Publication Date
EP2737107A1 EP2737107A1 (fr) 2014-06-04
EP2737107B1 true EP2737107B1 (fr) 2015-09-09

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ID=44736123

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EP11175295A Withdrawn EP2551375A1 (fr) 2011-07-26 2011-07-26 Composition de bain pour placage autocatalytique de nickel
EP12743909.9A Active EP2737107B1 (fr) 2011-07-26 2012-07-04 Composition de bain de nickelage autocatalytique

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EP11175295A Withdrawn EP2551375A1 (fr) 2011-07-26 2011-07-26 Composition de bain pour placage autocatalytique de nickel

Country Status (7)

Country Link
US (1) US20140150689A1 (fr)
EP (2) EP2551375A1 (fr)
JP (1) JP6053785B2 (fr)
KR (1) KR101936977B1 (fr)
CN (1) CN103946420B (fr)
TW (1) TWI555878B (fr)
WO (1) WO2013013941A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2551375A1 (fr) 2011-07-26 2013-01-30 Atotech Deutschland GmbH Composition de bain pour placage autocatalytique de nickel
US11685999B2 (en) 2014-06-02 2023-06-27 Macdermid Acumen, Inc. Aqueous electroless nickel plating bath and method of using the same
CN104152877B (zh) * 2014-07-17 2017-02-15 广东致卓精密金属科技有限公司 一种化学镀镍液
ES2639300T3 (es) 2014-12-16 2017-10-26 Atotech Deutschland Gmbh Composiciones de baño de chapado para el chapado no electrolítico de metales y aleaciones metálicas
SG11201706122SA (en) 2015-03-20 2017-10-30 Atotech Deutschland Gmbh Activation method for silicon substrates
EP3190208B1 (fr) * 2016-01-06 2018-09-12 ATOTECH Deutschland GmbH Bains de nickelage autocatalytique comprenant des aminonitriles et procédé de dépôt de nickel et d'alliages de nickel

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CH620710A5 (en) 1975-10-06 1980-12-15 Fedor Petrovich Potapov Process for chemical nickel-plating of workpieces having a catalytic surface, and installation for carrying out the process
GB2155041A (en) 1984-03-05 1985-09-18 Omi Int Corp Aqueous electroless nickel plating
EP1489201A2 (fr) 2003-06-18 2004-12-22 Raschig GmbH Alcoxylats d'alkylamines substitués par un groupe propanesulfonique ou 2-hydroxy-propanesulfonique, leur preparation et utilisation comme additives pour la déposition des couches métalliques
US20060264043A1 (en) 2005-03-18 2006-11-23 Stewart Michael P Electroless deposition process on a silicon contact
WO2010069810A1 (fr) 2008-12-19 2010-06-24 Basf Se Composition pour dépôt électrolytique de métaux comprenant un agent d'écoulement
EP2551375A1 (fr) 2011-07-26 2013-01-30 Atotech Deutschland GmbH Composition de bain pour placage autocatalytique de nickel

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Publication number Priority date Publication date Assignee Title
CH620710A5 (en) 1975-10-06 1980-12-15 Fedor Petrovich Potapov Process for chemical nickel-plating of workpieces having a catalytic surface, and installation for carrying out the process
GB2155041A (en) 1984-03-05 1985-09-18 Omi Int Corp Aqueous electroless nickel plating
EP1489201A2 (fr) 2003-06-18 2004-12-22 Raschig GmbH Alcoxylats d'alkylamines substitués par un groupe propanesulfonique ou 2-hydroxy-propanesulfonique, leur preparation et utilisation comme additives pour la déposition des couches métalliques
US20060264043A1 (en) 2005-03-18 2006-11-23 Stewart Michael P Electroless deposition process on a silicon contact
WO2010069810A1 (fr) 2008-12-19 2010-06-24 Basf Se Composition pour dépôt électrolytique de métaux comprenant un agent d'écoulement
EP2551375A1 (fr) 2011-07-26 2013-01-30 Atotech Deutschland GmbH Composition de bain pour placage autocatalytique de nickel

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H.-P. LIU ET AL.: "Effect of organic additives on the corrosion resistance properties of electroless nickel deposits", THIN SOLID FILMS, vol. 516, 2008, pages 1883 - 1889, XP022449729
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Also Published As

Publication number Publication date
TWI555878B (zh) 2016-11-01
EP2551375A1 (fr) 2013-01-30
KR101936977B1 (ko) 2019-01-09
CN103946420B (zh) 2015-11-25
US20140150689A1 (en) 2014-06-05
WO2013013941A1 (fr) 2013-01-31
EP2737107A1 (fr) 2014-06-04
CN103946420A (zh) 2014-07-23
JP6053785B2 (ja) 2016-12-27
KR20140041762A (ko) 2014-04-04
TW201309844A (zh) 2013-03-01
JP2014521834A (ja) 2014-08-28

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