DE102014105823A1 - Post-cleaning process of metallic contact elements - Google Patents

Post-cleaning process of metallic contact elements

Info

Publication number
DE102014105823A1
DE102014105823A1 DE102014105823.2A DE102014105823A DE102014105823A1 DE 102014105823 A1 DE102014105823 A1 DE 102014105823A1 DE 102014105823 A DE102014105823 A DE 102014105823A DE 102014105823 A1 DE102014105823 A1 DE 102014105823A1
Authority
DE
Germany
Prior art keywords
characterized
aqueous solution
ppm
solution according
surfactants
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Withdrawn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
DE102014105823.2A
Other languages
German (de)
Inventor
Alexander Meyerovich
Helmut Riechmann
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.)
HARTING AG & CO. KG, DE
Original Assignee
Harting KGaA
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 Harting KGaA filed Critical Harting KGaA
Priority to DE102014105823.2A priority Critical patent/DE102014105823A1/en
Publication of DE102014105823A1 publication Critical patent/DE102014105823A1/en
Application status is Withdrawn legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23GCLEANING OR DEGREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/20Other heavy metals
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
    • C11D11/0005Special cleaning and washing methods
    • C11D11/0011Special cleaning and washing methods characterised by the objects to be cleaned
    • C11D11/0023"Hard" surfaces
    • C11D11/0029Metals
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
    • C11D11/0005Special cleaning and washing methods
    • C11D11/0011Special cleaning and washing methods characterised by the objects to be cleaned
    • C11D11/0023"Hard" surfaces
    • C11D11/0047Electronic devices, e.g. PCBs, semiconductors
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0073Anticorrosion compositions
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34Pretreatment of metallic surfaces to be electroplated
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00Electroplating characterised by the article coated

Abstract

The invention relates to an aqueous solution for the pretreatment or post-cleaning of contact elements with a surface of a silicon-containing copper alloy, wherein the solution is alkaline, i. has a pH> 7, and contains at least one corrosion inhibitor. Ideally, the solution contains at least two different surfactants, wherein the surfactants are anionic surfactants and / or nonionic surfactants and / or amphoteric surfactants and / or block copolymers.

Description

  • The invention is based on an aqueous solution for the pretreatment or post-cleaning of contact elements with a surface made of a silicon-containing copper alloy.
  • Such solutions are used in galvanic coating processes.
  • State of the art
  • It is known that the surfaces of metallic workpieces are almost always, due to storage and manufacturing, contaminated with oils, fats, anticorrosion agents and often with material abrasion, grinding and polishing. A perfect surface refinement of non-ferrous metal surfaces, in particular galvanization of such workpieces, requires sufficient pre-treatment and cleaning. Depending on the requirements, pretreatment may smooth and eliminate material defects or cause special effects.
  • In non-ferrous metal or copper alloy cleaning, the use of aqueous, alkaline cleaning formulations of surfactant and builder components has prevailed to achieve clean surfaces that are required for subsequent refining processes.
  • Since, for example, after an electrolytic degreasing of a silicon-containing copper alloy, a thin silicon layer can interfere with the adhesion of a subsequent coating on the base material and it can lead to layer chipping, usually a subsequent cleaning or pretreatment of the material to be coated must take place.
  • task
  • It is known that in a surface cleaning in fluorine-containing solutions, the silicon particles remaining on the surface could be removed. But the use of such solutions is very questionable for occupational safety and environmental reasons.
  • The invention defined by the independent claim 1 forms an alternative to the currently used fluorine or fluoride-containing solutions.
  • Advantageous embodiments of the invention are specified in the subclaims.
  • It has surprisingly been found that a post-treatment or a pretreatment of a silicon-containing copper alloy surface cleaned in a strongly alkaline solution produces galvanically applied metallic coatings of very high quality and excellent adhesion thereto.
  • However, the surfaces of copper alloy workpieces in the strongly alkaline solutions are severely attacked. As a result, for example, the surface roughness is increased, which severely limits the universal applicability of these solutions. It has been found that the addition of special corrosion inhibitors largely prevents a corrosive attack of the copper surface in strongly alkaline solutions.
  • A subsequent cleaning or a pretreatment of workpieces with a silicon-containing copper alloy surface takes place in an aqueous solution. Such a solution is also called a post-cleaning solution. Advantageously, such a solution based on sodium hydroxide (NaOH) or potassium hydroxide (KOH).
  • In addition, an addition of corrosion inhibitor and anionic and / or nonionic surfactants is preferably present in the solution. This allows a uniform removal of the silicon-containing copper alloy surface with low average roughness.
  • One could also say that the surface is silicate-containing, since the silicon is also present in the oxidized state.
  • As already mentioned, the post-cleaning solutions which are alkaline according to the present invention contain corrosion inhibitors which reduce a negative effect on the non-ferrous metal surfaces. Without these corrosion inhibitors, the surfaces would be attacked with increasing alkalinity of the solutions, which may lead to a more or less significant weight change, occasionally associated with a gloss decrease of polished surfaces.
  • Advantageously, the following corrosion inhibitors are to be used: mercaptobenzothiazoles, alkylaminotriazoles, such as alkylaminotriazole in Fettsäurepolydiethanolamid (Texamin ® AT3) benzotriazoles, Alkylphenyltriazole, amino-alkyl-benzimidazole and / or phenylthioureas, amines such as monoethanolamine (MEA). All of the aforementioned corrosion inhibitors can also be used in a mixture with one another.
  • It has been found to be advantageous if the solution contains 5 to 1000 ppm (ppm: parts per million), preferably 10 to 200 ppm, of one or more corrosion inhibitors. Particularly preferred is the use of 20 ppm corrosion inhibitor in the solution. Here, a good corrosion protection is achieved with a sufficient surface coverage.
  • The post-cleaning solution used according to the invention preferably contains at least two different surfactants from the following surfactant groups. It is known that surfactants are compounds which reduce the interfacial tension of a solution. These are amphiphilic compounds with at least one hydrophobic and one hydrophilic moiety.
  • In the context of the invention, all surfactants such as, for example, anionic surfactants and / or nonionic surfactants, amphoteric surfactants and block copolymers (in particular of ethylene oxide and propylene oxide units) can be used.
  • By adding surfactants to the highly alkaline solution, the surface and interfacial tension can be significantly reduced. An example of the anionic surfactants is sodium 2-ethylhexyl sulfate. This wetting agent is highly effective, but low foaming for strongly alkaline and electrolyte-containing media.
  • The nonionic surfactants, such as, for example, the fatty alcohols, are generally well suited for reducing the surface tension of the aqueous solution according to the invention. They have the additional advantage that they foam little and thus prevent or reduce the undesirable foaming in the subsequent cleaning of the surface. In particular, foaming can reduce the circulation pump pressure in the plating bath.
  • Suitable nonionic surfactants are, for example: alkyl polyglycosides (eg octyl glycosides, hexyl glycosides), fatty alcohol ethoxylates having a chain length of 10-18 carbon atoms and 2-10 mol ethylene oxide (EO) / propylene oxide (PO) (eg HOESCH FA 42 LF, Ethylan CPG 660 ).
  • Supporting agents are so-called wetting agents, preferably ethoxylated fatty acid phosphates and fatty amine oxides.
  • Cocoamidopropylbetaines and / or cocopropylsulfobetaines are preferably used as amphoteric surfactants.
  • The content of anionic surfactants in the solution is preferably 15 to 500 ppm, more preferably 15 to 100 ppm, still more preferably 15 to 50 ppm.
  • Nonionic surfactants in the solution are preferably 15 to 500 ppm, more preferably 15 to 200 ppm, more preferably 25 to 100 ppm.
  • The ready-to-use solution preferably has a surface tension of less than 70 mN / m (millinewtons per meter), preferably less than 60 mN / m, more preferably less than 50 mN / m. The surface tension is determined by means of a tensiometer according to the so-called bubble pressure method.
  • The contact element to be treated is preferably exposed to the solution for between 10 seconds and 6 minutes.
  • It has been found that a treatment time between 10 seconds and two minutes in a temperature range between 50 to 90 ° C, particularly preferably between 70 to 85 ° C, is advantageous. In this case, the thin silicate-containing layer on the contact element is completely removed.
  • Compared with conventional pretreatment of the copper alloys in a degreasing, that is, the thin silicate-containing layer formed on the surface is removed. Thus, the solutions according to the invention for the post-purification of the silicon-containing copper alloys are very suitable.
  • For the subsequent cleaning of contact elements in aqueous systems or solutions, therefore, the dipping / flooding, spraying, brushing, ultrasound and electrolysis methods are used alone or in combination with one another.
  • Thanks to the solution according to the invention, surfaces containing silicon-containing copper alloys can be provided with metal coatings of nickel, copper, tin and their respective alloys.
  • The layer adhesion is tested by bending tests of the sheets, wherein the sheets are bent by about 180 °. The poor layer adhesion of Comparative Examples 1 and 2 is shown in the bending test by flaking off the galvanized layer at the kink point. Unlike conventional aqueous metal treatment methods, the coating properties are not adversely affected by the components introduced into the bath by the aftertreatment, in particular by the corrosion inhibitor, surfactants or alkaline solution.

Claims (14)

  1. Aqueous solution for pretreatment or post-cleaning of contact elements with a surface made of a silicon-containing copper alloy, characterized in that • the solution has a pH value> 7 and contains at least one corrosion inhibitor.
  2. Aqueous solution according to claim 1, characterized in that the solution has a pH ≥ 10.
  3. Aqueous solution according to one of the preceding claims, characterized in that the solution contains a corrosion inhibitor mercaptobenzothiazoles, alkylaminotriazoles, benzotriazoles, alkylphenyltriazoles, amino-alkyl-benzimidazoles and / or phenylthioureas, amines or a mixture of the aforementioned corrosion inhibitors.
  4. Aqueous solution according to one of the preceding claims, characterized in that the solution contains 5 to 1000 ppm of one or more corrosion inhibitors.
  5. Aqueous solution according to any one of claims 1-3, characterized in that the solution contains 10 to 200 ppm of one or more corrosion inhibitors.
  6. Aqueous solution according to any one of claims 1-3, characterized in that the solution contains 15 to 25 ppm corrosion inhibitor.
  7. Aqueous solution according to one of the preceding claims, characterized in that the solution contains at least two different surfactants.
  8. Aqueous solution according to the preceding claim, characterized in that the surfactants are anionic surfactants and / or nonionic surfactants and / or amphoteric surfactants and / or block copolymers.
  9. Aqueous solution according to claim 8, characterized in that are provided as nonionic surfactants alkylpolyglycosides and / or fatty alcohol ethoxylates.
  10. Aqueous solution according to claim 8, characterized in that cocoamidopropylbetaines and / or cocopropylsulfobetaines are provided as amphoteric surfactants.
  11. Aqueous solution according to one of the preceding claims, characterized in that the solution contains wetting agents, preferably ethoxylated fatty acid phosphates and / or fatty amine oxides.
  12. Aqueous solution according to one of the preceding claims, characterized in that the content of anionic surfactants in the solution is 15 to 500 ppm, but preferably 15 to 100 ppm, more preferably 15 to 50 ppm.
  13. Aqueous solution according to one of the preceding claims, characterized in that the content of nonionic surfactants is 15 to 500 ppm, but preferably 15 to 200 ppm, more preferably 25 to 100 ppm.
  14. Aqueous solution according to one of the preceding claims, characterized in that the surface tension of the solution is less than 70 mN / m, but preferably less than 60 mN / m, more preferably less than 50 mN / m.
DE102014105823.2A 2014-04-25 2014-04-25 Post-cleaning process of metallic contact elements Withdrawn DE102014105823A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE102014105823.2A DE102014105823A1 (en) 2014-04-25 2014-04-25 Post-cleaning process of metallic contact elements

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102014105823.2A DE102014105823A1 (en) 2014-04-25 2014-04-25 Post-cleaning process of metallic contact elements
PCT/DE2015/100080 WO2015161842A1 (en) 2014-04-25 2015-03-02 After-cleaning method for metallic contact elements

Publications (1)

Publication Number Publication Date
DE102014105823A1 true DE102014105823A1 (en) 2015-10-29

Family

ID=52807472

Family Applications (1)

Application Number Title Priority Date Filing Date
DE102014105823.2A Withdrawn DE102014105823A1 (en) 2014-04-25 2014-04-25 Post-cleaning process of metallic contact elements

Country Status (2)

Country Link
DE (1) DE102014105823A1 (en)
WO (1) WO2015161842A1 (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1078405B (en) * 1954-09-16 1960-03-24 Geigy Ag J R Corrosion inhibitor for protection of copper and its Leigierungen
DE3635636A1 (en) * 1985-10-23 1987-04-23 Ciba Geigy Ag corrosion inhibiting process
DE102004045297A1 (en) * 2004-09-16 2006-03-23 Basf Ag A method of treating metallic surfaces using low methane sulfonic acid based formulations

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4119102A1 (en) * 1991-06-10 1992-12-17 Henkel Kgaa Method for pre-treating buntmetal surfaces before a galvanic metal coating
US6723691B2 (en) * 1999-11-16 2004-04-20 Advanced Technology Materials, Inc. Post chemical-mechanical planarization (CMP) cleaning composition
US7435712B2 (en) * 2004-02-12 2008-10-14 Air Liquide America, L.P. Alkaline chemistry for post-CMP cleaning
JP4708485B2 (en) * 2009-03-31 2011-06-22 Jx日鉱日石金属株式会社 Cu-Co-Si based copper alloy for electronic materials and method for producing the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1078405B (en) * 1954-09-16 1960-03-24 Geigy Ag J R Corrosion inhibitor for protection of copper and its Leigierungen
DE3635636A1 (en) * 1985-10-23 1987-04-23 Ciba Geigy Ag corrosion inhibiting process
DE102004045297A1 (en) * 2004-09-16 2006-03-23 Basf Ag A method of treating metallic surfaces using low methane sulfonic acid based formulations

Also Published As

Publication number Publication date
WO2015161842A1 (en) 2015-10-29

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Legal Events

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R012 Request for examination validly filed
R016 Response to examination communication
R083 Amendment of/additions to inventor(s)
R081 Change of applicant/patentee

Owner name: HARTING AG & CO. KG, DE

Free format text: FORMER OWNER: HARTING KGAA, 32339 ESPELKAMP, DE

R119 Application deemed withdrawn, or ip right lapsed, due to non-payment of renewal fee