EP1360346A2 - Saures bad zur galvanischen abscheidung von einer zink-manganlegierung - Google Patents

Saures bad zur galvanischen abscheidung von einer zink-manganlegierung

Info

Publication number
EP1360346A2
EP1360346A2 EP02702457A EP02702457A EP1360346A2 EP 1360346 A2 EP1360346 A2 EP 1360346A2 EP 02702457 A EP02702457 A EP 02702457A EP 02702457 A EP02702457 A EP 02702457A EP 1360346 A2 EP1360346 A2 EP 1360346A2
Authority
EP
European Patent Office
Prior art keywords
manganese
bath
zinc
agent
ions
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.)
Withdrawn
Application number
EP02702457A
Other languages
English (en)
French (fr)
Inventor
Lionel Thiery
Gian Luigi Schiavon
Nicolas Pommier
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.)
Coventya SAS
Original Assignee
Coventya SAS
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 Coventya SAS filed Critical Coventya SAS
Publication of EP1360346A2 publication Critical patent/EP1360346A2/de
Withdrawn legal-status Critical Current

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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc

Definitions

  • the present invention relates to an electrolysis bath consisting of an acidic aqueous solution for depositing an alloy of zinc and manganese in particular on steel.
  • Zinc-manganese deposits have shown their superiority compared to other alloyed zinc by their superior corrosion resistance in a natural atmosphere.
  • Surface analyzes after exposure to natural corrosion have highlighted the presence of a ⁇ -Mn 2 ⁇ 3 manganese oxide which would act as a passivation layer. This type of oxide would block oxygen reduction and therefore decrease corrosion of the coating.
  • the known zinc-manganese electrolytic deposition processes are composed of an acidic aqueous solution either based on sodium citrate or based on ammonium chloride.
  • the replacement of ammonium chloride by an alkali metal salt based on chloride, such as sodium chloride or potassium chloride also does not make it possible to obtain deposits with sufficient concentrations of manganese in the deposit.
  • the use of complexing agents such as tartaric acid or gluconic acid makes it possible to obtain deposits having high manganese concentrations in the deposit.
  • This type of bath has the disadvantage of working at a pH between 6.3 and 6.9, which requires adding sodium hydroxide to the bath.
  • the zinc and manganese ions are not stable, that is to say that they are in the form of precipitates of zinc and manganese hydroxides. Therefore to avoid the formation of these species it is necessary to complex the zinc ions and the manganese ions with complexing agents such as citric or tartaric acid.
  • complexing agents such as citric or tartaric acid.
  • the local increase in pH occurring during the reduction of zinc and manganese may lead to the formation of zinc and manganese hydroxides. This phenomenon is accentuated if one works at a very low acid pH, that is to say of the order of 6.3 to 6.9.
  • the present invention relates to a stable electrolysis bath, consisting of an acidic aqueous solution, making it possible to obtain a deposit of zinc and manganese having a good manganese content and a good yield, without having to carry out a particular treatment of the waters. of rejection.
  • This acid bath therefore does not require the presence of complexing agents and allows to use smaller amounts of boric acid than those used in GB 2 351 503
  • the subject of the invention is a bath consisting of an acidic aqueous solution free of ammonium ion, fluoroborate ion and citrate ion and comprising per liter
  • Mn 2+ ions from 20 to 100 g of Mn 2+ ions, characterized in that it comprises a buffering agent maintaining the pH at a value between 4.0 and 6.0 and, preferably, between 4.5 and 6 and a another agent, distinct from the buffering agent, making it possible to approximate the deposition potentials of zinc and manganese.
  • the invention also relates to a method of electroplating an alloy of zinc and manganese using the bath according to the invention.
  • an acidic aqueous solution is used, free from ammonium ion, fluoroborate ion and citrate ion, containing:
  • the zinc ion may be present in the form of a soluble salt such as zinc sulphate or zinc chloride.
  • the manganese ion may be present in the form of a soluble salt such as manganese sulphate or manganese acetate or manganese chloride.
  • a conductive salt in particular of an alkali metal such as sodium chloride, potassium chloride, sodium sulfate or potassium sulfate. Its concentration in the electrolytic bath is preferably from 100 to 250 g / L.
  • a buffering agent to control the pH was obtained by citrate, tartrate or gluconate ions and ammonium ions.
  • This buffering agent can be boric acid and its concentration is of the order of 5 to 40 g / L.
  • Other buffers can be used such as hydrogenophthalate, dihydrogenophosphate and acetate buffers.
  • a sufficient quantity of hydronium ions is sought in order to have a pH of between 4.8 and 5.5.
  • At least one potential approximation agent or addition agent in order to shift the electrochemical potential of zinc towards that of manganese and thus allow the codeposition of zinc and manganese. This role was played by ammonium ions and citrate ions in the other baths.
  • the potentials of the two redox systems can be brought together by complexing the metal ions. Complexation modifies the electrochemical potential of each of the couples and makes it possible to approximate the polarization curves.
  • Ri aryloxy group, in particular phenoxy or naphthoxy, aryloxyalkoxy group, in particular phenoxyalkoxy or naphthoxyalkoxy, where the alkoxy part of the aryloxyalkoxy radical has from 1 to 6 carbon atoms, alkylaryl group, in particular alkylphenyl or alkylnaphthyl where the alkyl part of the alkylaryl radical has 1 to 12 carbon atoms, alkylaryloxy group, in particular alkylphenoxy or alkylnaphthoxy, or alkylaryloxyalkoxy group, in particular alkylphenoxyalkoxy or alkylnaphthoxyalkoxy.
  • linear or branched alkyl groups preferably having from 1 to 6 carbon atoms.
  • R1 is aryloxyalkoxy, especially phenoxyalkoxy or naphthoxyalkoxy. Ori-les preferably uses it at a concentration between 0.5 and 10 g / L
  • synergistic agents are the compounds having the following general formula:
  • R -H, or a linear or branched alkyl group having up to 6 carbon atoms
  • a brightening agent is added to the electrolysis bath to obtain a bright deposit and to improve the codeposition of the alloyed metal, manganese.
  • These brighteners are compounds which have the general formula:
  • R 5 ⁇ -H, - CH 3 , aryl group, in particular phenyl, alkylphenyl or alkenylphenyl such as: -C 6 H 5 , CH 3 -C 6 H -, CH 3 -CH 2 -C 6 H 4 -, -CH ⁇ CH- C 6 H5, or naphthyl group.
  • aryl group in particular phenyl, alkylphenyl or alkenylphenyl such as: -C 6 H 5 , CH 3 -C 6 H -, CH 3 -CH 2 -C 6 H 4 -, -CH ⁇ CH- C 6 H5, or naphthyl group.
  • R 6 ⁇ -H or alkyl such as -CH 3 , -CH2-CH3, -CH2-CH2-CH3 (linear or branched alkyl and alkenyl groups preferably having from 1 to 6 carbon atoms).
  • citrate or ammonium ions previously played two different roles.
  • the role of buffering agent and the role of agent for bringing potentials to different compounds we are free from a constraint for the choice of agent for bringing together potentials and we can now use a complexing agent as such less annoying in rejections than those to which one was forced to resort.
  • Example 1.1 The deposit is made at 1.5 A / dm 2 for 30 minutes. The deposit is then analyzed by Fluorescence X or by dissolution of the deposit in dilute hydrochloric acid and assay by Atomic Absorption Spectrometry to verify the presence of manganese in the deposit. Comparative example 1 Example 1.1
  • ammonium ion strongly complexes metal ions such as Ni 2+ and Cu 2+ ions (ions which may be present in a surface treatment chain) and are therefore not precipitated as metallic hydroxide during the neutralization process. /precipitation.
  • baths containing ammonium ions are undesirable.
  • the release of the ammonium ion itself constitutes an environmental nuisance.
  • Example ⁇ (according to the invention)
  • This compound is marketed by the company SABO under the name of Sabosol NFE-8. We varied its concentration in the bath from 0.5g / L to 10g / L.
  • the deposit contains manganese, that is to say that we have made a deposit of zinc and manganese.
  • the amount of manganese in the deposit increases with the concentration of addition agent, the bath is stable for several months, that is to say that there is no bacterial proliferation in the bath, nor precipitation crystalline.
  • This compound is marketed by the company RASCHIG GMBH Ludwigshafen Germany under the name of Ralufon NAPE 14-90. We varied its concentration in the bath from 0.5g / L to 10g / L. In all cases :
  • the deposit contains manganese, that is to say that we have made a deposit of zinc and manganese.
  • the amount of manganese in the deposit increases with the concentration of addition agent,
  • the bath is stable for several months, that is to say that there is no bacterial proliferation in the bath, nor any crystalline precipitation.
  • This compound is marketed by BASF under the name of Lugalvan BNO 24.
  • the deposit contains manganese, that is to say that we have made a deposit of zinc and manganese.
  • the amount of manganese in the deposit increases with the concentration of addition agent, the bath is stable for several months, that is to say that there is no bacterial proliferation in the bath, nor precipitation crystalline.
  • Zinc chloride 60 g / L Manganese chloride monohydrate 60 g / L Potassium chloride 240 g / L
  • This compound is marketed by the company CYTEC INDUSTRIES INC. under the name of Aerosol OS (West Paterson New Jersey E.U.A.).
  • This compound is marketed by the company RASCHIG under the name of Ralufon N 9.
  • the deposit contains manganese, that is to say that we have made a deposit of zinc and manganese,
  • the bath is stable for several months, that is to say that there is no bacterial proliferation in the bath, nor any crystalline precipitation.
  • the deposit contains manganese, that is to say that we have made a deposit of zinc and manganese.
  • the deposit contains even more manganese than in Example 2 and 3, or the bath only contained the agent for bringing potentials together.
  • the use of synergists alone did not make it possible to co-deposit zinc and manganese (examples 8 and 9).
  • the use of synergistic agents in a bath containing the addition agents makes it possible to obtain deposits having even more manganese - the bath is stable for several months, that is to say that one does not observe no bacterial growth in the bath, no crystal precipitation.
  • the concentration in the bath is 8 g / L
  • the deposit contains manganese, that is to say that we have carried out a deposit of zinc and manganese, the manganese being present in a greater content than if we only use the addition agent. This synergistic effect is unexpected.

Landscapes

  • 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)
  • Electrolytic Production Of Metals (AREA)
EP02702457A 2001-02-06 2002-02-06 Saures bad zur galvanischen abscheidung von einer zink-manganlegierung Withdrawn EP1360346A2 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0101555 2001-02-06
FR0101555A FR2820439B1 (fr) 2001-02-06 2001-02-06 Bain acide pour l'electrodeposition d'un alliage zinc-manganese
PCT/FR2002/000459 WO2002063071A2 (fr) 2001-02-06 2002-02-06 Bain acide pour l'electrodeposition d'un alliage zinc-manganese

Publications (1)

Publication Number Publication Date
EP1360346A2 true EP1360346A2 (de) 2003-11-12

Family

ID=8859654

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02702457A Withdrawn EP1360346A2 (de) 2001-02-06 2002-02-06 Saures bad zur galvanischen abscheidung von einer zink-manganlegierung

Country Status (5)

Country Link
US (1) US7070689B2 (de)
EP (1) EP1360346A2 (de)
JP (1) JP4159879B2 (de)
FR (1) FR2820439B1 (de)
WO (1) WO2002063071A2 (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9840788B2 (en) * 2014-05-30 2017-12-12 Applied Materials, Inc. Method for electrochemically depositing metal on a reactive metal film
US9828687B2 (en) * 2014-05-30 2017-11-28 Applied Materials, Inc. Method for electrochemically depositing metal on a reactive metal film
US11066752B2 (en) 2018-02-28 2021-07-20 The Boeing Company Compositionally modulated zinc-manganese multilayered coatings

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5794590A (en) * 1980-12-04 1982-06-12 Toshikatsu Watabe High corrosion resistant zinc plating method
US4898652A (en) * 1986-03-03 1990-02-06 Omi International Corporation Polyoxalkylated polyhydroxy compounds as additives in zinc alloy electrolytes
JPH0826474B2 (ja) * 1989-08-31 1996-03-13 日本鋼管株式会社 生産性に優れた亜鉛―マンガン合金の電気めつき方法
JPH0565674A (ja) * 1991-09-09 1993-03-19 Nkk Corp 亜鉛−マンガン合金層を有するアルミニウム板およびアルミニウム合金板
FR2762331B1 (fr) * 1997-04-22 1999-09-24 Peugeot Composition pour le depot electrolytique d'un alliage de zinc-manganese, procede de depot d'une telle composition et revetement ainsi obtenu
GB9910681D0 (en) * 1999-05-07 1999-07-07 Enthone Omi Benelux Bv Alloy plating
US6387229B1 (en) * 1999-05-07 2002-05-14 Enthone, Inc. Alloy plating

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO02063071A2 *

Also Published As

Publication number Publication date
JP4159879B2 (ja) 2008-10-01
US7070689B2 (en) 2006-07-04
FR2820439B1 (fr) 2004-04-09
WO2002063071A3 (fr) 2003-03-13
JP2004524441A (ja) 2004-08-12
US20040050712A1 (en) 2004-03-18
FR2820439A1 (fr) 2002-08-09
WO2002063071A2 (fr) 2002-08-15

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