EP0227518A1 - Hydrazin enthaltendes Bad zum stromlosen Abscheiden von Nickel und/oder Kobalt und Verfahren zu dessen Herstellung - Google Patents

Hydrazin enthaltendes Bad zum stromlosen Abscheiden von Nickel und/oder Kobalt und Verfahren zu dessen Herstellung Download PDF

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Publication number
EP0227518A1
EP0227518A1 EP86402528A EP86402528A EP0227518A1 EP 0227518 A1 EP0227518 A1 EP 0227518A1 EP 86402528 A EP86402528 A EP 86402528A EP 86402528 A EP86402528 A EP 86402528A EP 0227518 A1 EP0227518 A1 EP 0227518A1
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EP
European Patent Office
Prior art keywords
nickel
bath according
bath
cobalt
ethylenediamine
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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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EP86402528A
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English (en)
French (fr)
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EP0227518B1 (de
Inventor
Pierre Josso
Isabelle Gossart
Claude Duret-Thual
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Office National dEtudes et de Recherches Aerospatiales ONERA
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Office National dEtudes et de Recherches Aerospatiales ONERA
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    • 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

Definitions

  • the invention relates to the chemical deposition of nickel and / or cobalt by autocatalytic reduction.
  • the nickel and / or cobalt deposits obtained from these baths are not pure. They indeed contain phosphorus or boron from the reducing agent, as well as elements from stabilizers: sulfur and / or heavy metals, for example thallium.
  • Patent No. 2,531,103 of the Applicant proposes baths making it possible to obtain deposits free of impurities from the stabilizers, and intended in particular for the treatment of turbine blades for aeronautical applications, these impurities being very troublesome for these applications and cannot be removed by further processing.
  • the deposits obtained still contain phosphorus or boron coming from phosphorus or boron reducers and these impurities are troublesome for the applications considered; it is therefore necessary to remove them after the deposition operation.
  • Hydrazine meets these conditions, its oxidation by nickel or cobalt ions exclusively leading to the formation of hydrogen and nitrogen, which are released in the gaseous state.
  • Nickel and / or cobalt chemical deposition baths containing hydrazine as a reducing agent are described in an article by Dini and Coronado published in Plating Vo. 54, p. 385 (1967), and in U.S. Patent No. 3,198,659.
  • An object of the invention is to provide baths for the chemical deposition of nickel and / or cobalt which can be used industrially and which make it possible to obtain very pure deposits of considerable thickness.
  • Another object is to provide hydrazine baths for the chemical deposition of nickel and / or cobalt which can be used industrially and which leads to deposits of considerable thickness.
  • the inventors studied the equilibria and the chemical reactions taking place in hydrazine baths and led to the formulation of the hypotheses set out below.
  • the nickel and / or cobalt ions are complexed concurrently by hydrazine and by the complexing agent proper from the bath, the partition coefficient between the hydrazine and the complexing agent being determined by the dissociation constants of the two complexing reactions.
  • the subject of the invention is a bath for the chemical deposition of nickel and / or cobalt, comprising a compound of the metal (or metals) to be deposited, a reducing agent, at least one complexing metal and at least one stabilizer.
  • the bath is chosen so that the anions which it contains or which are produced during its use are almost exclusively hydroxyl ions.
  • said compound, the reducing agent and the complexing agent are such that their anions, as well as the anions produced during the use of the bath, are essentially hydroxyl ions.
  • the reducing agent being hydrazine
  • said compound is nickel-II-tri (ethylenediamine) hydroxide and / or cobalt-II-tri-ethylenediamine) hydroxide of formula M (NH2-C2H4-NH2) 3 (OH) 2, in which M represents nickel and / or cobalt, and ethylenediamine plays the role of the complexing agent.
  • the subject of the invention is a bath for the chemical deposition of nickel and / or cobalt, comprising a compound of the metal (or metals) to be deposited, a reducing agent consisting of hydrazine, a metal complexing agent , and at least one stabilizer, characterized in that said compound is nickel-II-tri (ethylenediamine) hydroxide and / or cobalt-II-tri (ethylenediamine) hydroxide of formula M (NH2C2H4-NH2) 3 (OH) 2 , in which M represents nickel and / or cobalt, ethylenediamine playing the role of the complexing agent.
  • Nickel (or cobalt) II-tri (ethylenediamine) hydroxide is perfectly compatible with hydrazine and their joint use allows the bath to operate for a practically unlimited period by addition continuous of the metallic compound and the reducing agent, the ethylenediamine concentration not intervening in the deposition mechanism as long as this body is in excess, from which it results the possibility of obtaining very pure and thick deposits.
  • the bath according to the invention is preferably brought to a pH greater than 11 by an basifying agent which can be sodium hydroxide.
  • the bath according to the invention allows the inclusion in the deposit of particles, for example of alumina Al 2 O 3 or of yttrin Y 2 O 3 , contained in the bath. Thanks to the regularity over time of the characteristics of the bath, a uniform distribution of the particles is obtained in the thickness of the deposit.
  • the subject of the invention is also a method of manufacturing a bath as described above, in which an alkaline solution of M (NH2C2H4-NH2) 3 (OH) 2 ', called the mother solution, is prepared, and therein then add the stabilizers and hydrazine.
  • FIGS. 1 to 6 are micrographic sections of chemical deposits obtained by the use of the invention.
  • the initial metal salt is a pure salt for electroplating.
  • the choice of anion (designated by A) associated with the cation is indifferent and left to the choice of a person skilled in the art (chloride, sulfate or the like).
  • the starting salt is the basic carbonate of M, commonly used in the art for the correction of the pH of electrolytic baths with nickel and / or cobalt sulfamate.
  • the advantage presented by the use of such a salt lies in its intrinsic purity, due to its method of preparation. It is treated directly with anhydrous ethylenediamine in an amount 10% greater than the stoichiometric amount required and the reaction takes place:
  • the solution obtained is diluted to half.
  • Example 1 the anion of the initial salt is indifferent; the MA 2 solution is prepared in the same way. To this solution is added a large excess of oxalic acid which causes precipitation of M oxalate according to the reaction:
  • the temperature of the bath is maintained between 88 and 92 ° C.
  • the deposition rate is then between 10 and 15 ⁇ m.h -1 .
  • Figure 1 is a photograph of a deposit obtained on a brass substrate, magnified 500 times.
  • the deposit of pure nickel obtained is light gray, of regular thickness and of a hardness of approximately 450 HK (or Knoop hardness) under load of 50 g.
  • the temperature is maintained between 88 and 92 ° C.
  • the deposition reaction starts spontaneously, even on copper alloy substrates.
  • the weight gain is approximately 115 mg.cm -2 .h -1 , which corresponds to a growth rate of the deposit of approximately 130 ⁇ m.h -1 .
  • the deposit obtained is black and does not reflect light. metallographic observation of a section of this deposit shows that it is porous (see Figure 2 which represents a photograph magnified 100 times of a deposit obtained on a brass substrate).
  • the hardness measured on the gross bath deposit amounts to approximately 400 HK (or 450 HV, Vickers hardness), under a load of 50 g.
  • This bath contains thallium ions and consequently leads to the presence of traces of thallium in the deposit.
  • these baths thallium are not suitable for aerospace applications mentioned above. However, they can be of great interest in other applications, because of their longevity, regularity, thickness, physical and mechanical characteristics of the deposits they allow to obtain, and the possibility of including in them particles uniformly distributed.
  • a bath comprising, as stabilizer, thallium sulfate.
  • This bath differs from the previous one in that the nickel-II-tri (ethylenediamine) hydroxide is replaced by an equivalent amount of cobalt-II-tri (ethylenediamine) hydroxide, and in that 1.7 mol.l -1 are added. ethylenediamine.
  • the temperature of the bath is maintained between 78 and 82 ° C.
  • the deposition rate is between 25 and 30 ⁇ m.h -1 .
  • FIG. 3 The photograph in FIG. 3, magnified 500 times, illustrates the deposit of cobalt obtained on a brass substrate.
  • This deposit is semi-gloss, dense and regular, with a hardness of approximately 350 HK, under a load of 50 g.
  • This example illustrates a nickel deposition bath containing alumina particles.
  • the temperature is maintained between 88 and 92 ° C.
  • the deposition rate is around 35 ⁇ m.h -1 .
  • the deposit is black.
  • An examination on a metallographic section shows alumina particles included in the nickel deposit (see FIG. 4 which represents a photograph magnified 700 times of a deposit obtained on a brass substrate, the alumina having been added after 20 minutes of deposit).
  • the hardness of this deposit is approximately 400 HV, under a load of 50 g, comparable to that obtained for the deposit without alumina; and as in Example 5, the deposit is porous.
  • the temperature is maintained between 88 and 92 ° C.
  • the deposition reaction starts spontaneously, even on substrates made of copper alloys.
  • the deposition rate is approximately 20 ⁇ m.h -1 .
  • the deposit is dark gray, dense and regular in color (see FIG. 5 which represents a 750-fold enlarged photograph of two successive deposits obtained on a brass substrate, without any surface preparation between them).
  • Example 8 The bath of Example 8 is resumed, to which 20 grams per liter of yttrin particles with a particle size of between 0.5 and 1.5 microns are added.
  • the temperature is maintained between 88 and 92 ° C and the bath is stirred by means of a rotary agitator at about 800 revolutions per minute.
  • the deposition rate is between 10 and 15 ⁇ m.h -1 .
  • the deposit obtained is dark gray, dense and regular: a metallographic examination shows the yttrin particles enclosed in a nickel matrix (see FIG. 6 which represents a photograph 950 times magnified of a deposit obtained on a mild steel substrate) .
  • the temperature is maintained between 78 and 82 ° C.
  • the deposition rate is 18.1 ⁇ m.h -1
  • a deposit with a thickness of 13.2 ⁇ m of a nickel-cobalt alloy was produced, as shown by the qualitative analysis by energy dispersive spectroscopy of the scanning electron microscope.
  • the content of occluded gas in the various deposits obtained is relatively low, which causes little tension in the metal layers.
  • the oxygen, nitrogen and hydrogen contents of the deposit of Example 6 are respectively 429, 542 and 9 ppm, significantly lower than the minimum values cited in the aforementioned article by Dini and Coronado, namely 900 , 2410 and 150 ppm.
  • the nickel deposition rate which is around 15 ⁇ m.h -1 for dense deposits, can be increased by adding thallium. Deposition rates of 130 ⁇ m.h -1 were thus obtained. In this case, the deposits are porous and black.

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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)
  • Inorganic Compounds Of Heavy Metals (AREA)
EP86402528A 1985-11-22 1986-11-13 Hydrazin enthaltendes Bad zum stromlosen Abscheiden von Nickel und/oder Kobalt und Verfahren zu dessen Herstellung Expired - Lifetime EP0227518B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8517339 1985-11-22
FR8517339A FR2590595B1 (fr) 1985-11-22 1985-11-22 Bain a l'hydrazine pour le depot chimique de nickel et/ou de cobalt, et procede de fabrication d'un tel bain.

Publications (2)

Publication Number Publication Date
EP0227518A1 true EP0227518A1 (de) 1987-07-01
EP0227518B1 EP0227518B1 (de) 1990-07-25

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EP86402528A Expired - Lifetime EP0227518B1 (de) 1985-11-22 1986-11-13 Hydrazin enthaltendes Bad zum stromlosen Abscheiden von Nickel und/oder Kobalt und Verfahren zu dessen Herstellung

Country Status (5)

Country Link
US (1) US4844739A (de)
EP (1) EP0227518B1 (de)
JP (1) JPS62202080A (de)
DE (1) DE3672977D1 (de)
FR (1) FR2590595B1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0357684A4 (de) * 1987-07-20 1990-01-08 Gen Electric Elektrofreie nickelplattierungszusammensetzung und verfahren zu deren herstellung und verwendung.

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06104903B2 (ja) * 1988-08-19 1994-12-21 上村工業株式会社 無電解複合めっき浴及びめっき方法
JP2525521B2 (ja) * 1991-06-25 1996-08-21 日本リーロナール株式会社 無電解スズ―鉛合金めっき浴
US6183546B1 (en) * 1998-11-02 2001-02-06 Mccomas Industries International Coating compositions containing nickel and boron
FR2787472B1 (fr) 1998-12-16 2001-03-09 Onera (Off Nat Aerospatiale) Procede pour produire une poudre d'alliage metallique de type mcraly et revetements obtenus avec cette poudre
WO2001066825A1 (en) * 2000-03-08 2001-09-13 Mccomas, Edward Coating compositions containing nickel and boron
KR100859259B1 (ko) * 2005-12-29 2008-09-18 주식회사 엘지화학 캡층 형성을 위한 코발트 계열 합금 무전해 도금 용액 및이를 이용하는 무전해 도금 방법
US7794530B2 (en) * 2006-12-22 2010-09-14 Lam Research Corporation Electroless deposition of cobalt alloys

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3416955A (en) * 1965-01-13 1968-12-17 Clevite Corp Electroless cobalt plating bath
FR2341671A1 (fr) * 1976-02-17 1977-09-16 Basf Wyandotte Corp Cathode pour cellule d'electrolyse a chlore-alcali

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4265943A (en) * 1978-11-27 1981-05-05 Macdermid Incorporated Method and composition for continuous electroless copper deposition using a hypophosphite reducing agent in the presence of cobalt or nickel ions
DE3049417A1 (de) * 1980-12-30 1982-07-29 Siemens AG, 1000 Berlin und 8000 München "bad und verfahren zum stromlosen abscheiden von nickelueberzuegen"
US4368223A (en) * 1981-06-01 1983-01-11 Asahi Glass Company, Ltd. Process for preparing nickel layer
JPS60248882A (ja) * 1984-05-24 1985-12-09 Aisin Seiki Co Ltd 高リン含有ニツケル合金の無電解めつき浴

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3416955A (en) * 1965-01-13 1968-12-17 Clevite Corp Electroless cobalt plating bath
FR2341671A1 (fr) * 1976-02-17 1977-09-16 Basf Wyandotte Corp Cathode pour cellule d'electrolyse a chlore-alcali

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PLATING, vol. 54, no. 4, avril 1967, pages 385-390; J.W: DINI et al.: "Thick nickel deposits of high purity by electroless methods" *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0357684A4 (de) * 1987-07-20 1990-01-08 Gen Electric Elektrofreie nickelplattierungszusammensetzung und verfahren zu deren herstellung und verwendung.
EP0357684A1 (de) * 1987-07-20 1990-03-14 Coors Porcelain Company Elektrofreie nickelplattierungszusammensetzung und verfahren zu deren herstellung und verwendung

Also Published As

Publication number Publication date
FR2590595A1 (fr) 1987-05-29
US4844739A (en) 1989-07-04
EP0227518B1 (de) 1990-07-25
FR2590595B1 (fr) 1988-02-26
JPS62202080A (ja) 1987-09-05
DE3672977D1 (de) 1990-08-30
JPH0156144B2 (de) 1989-11-29

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