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EP0967301B1 - Pickling-activating solution for pre-treatment of aluminium-steel composites before electroless tin plating - Google Patents

Pickling-activating solution for pre-treatment of aluminium-steel composites before electroless tin plating Download PDF

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Publication number
EP0967301B1
EP0967301B1 EP99111464A EP99111464A EP0967301B1 EP 0967301 B1 EP0967301 B1 EP 0967301B1 EP 99111464 A EP99111464 A EP 99111464A EP 99111464 A EP99111464 A EP 99111464A EP 0967301 B1 EP0967301 B1 EP 0967301B1
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EP
European Patent Office
Prior art keywords
pickling
solutions according
aluminum
activation
aluminium
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EP99111464A
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German (de)
French (fr)
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EP0967301A3 (en
EP0967301A2 (en
Inventor
Jan Eberhardt
Dieter Dr. Guhl
Frank Honselmann
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Evonik Operations GmbH
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TH Goldschmidt AG
Goldschmidt GmbH
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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
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
    • C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
    • C23C18/1837—Multistep pretreatment
    • C23C18/1844—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • 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
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions

Definitions

  • the invention relates to an aqueous preparation for pickling and activation of aluminum-steel composites before one electroless plating.
  • aluminum-steel composite materials are plain bearings, bushings, thrust washers, Dry sliding bearings etc. for pumps, motors and gears. After pickling activation, the aluminum and Steel surfaces of the substrate during a subsequent dip tinning even, particularly adhesive tin coatings achieved.
  • EP-A-0 278 752 discloses substrates made of pure aluminum alloys and also aluminum-steel composite metals after one Pretreatment consisting of degreasing and pickling with acid Tin tin electrolytes in an exchange process.
  • DE-A-29 17 019 describes a method for metallization of aluminum-steel composite material.
  • the used here Bath consists of a mineral acid, a source of fluoride ions, fluoride-containing ions or their mixtures, and a source for stannous ions in a concentration of approximately 1 to 75 g / l. Before the composite material with a mineral acid containing fluoride ions activated.
  • the present invention is therefore concerned with the technical Problem, the pretreatment of the aluminum-steel composite to optimize.
  • the task of present invention therein using the known Dip tinning baths uniform, adhesive tin coatings both on the aluminum as well as on the steel surfaces of the Manufacture substrate.
  • Dilute sulfuric acid is suitable for pickling iron alloys, causes, however, at temperatures of up to 70 ° C and Diving times of a few minutes, no noticeable attack on Aluminum.
  • Hexafluorosilicic acid cleans and activates aluminum alloys, without significantly attacking iron surfaces.
  • the combination of both acids becomes the complex substrate structure made of two alloys with very different chemical and physical properties. Examples of aluminum-steel composite materials are plain bearings, bushings, thrust washers, Dry sliding bearings etc. for pumps, motors and gears.
  • nitrate and / or nitrite ions proven positive.
  • wetting agents are suitable all surfactants well wetting the substrate, which have a sufficient chemical resistance in the pickling activation electrolyte have.
  • Wetting agents such as they are used in immersion tinning baths which are used in EP-A-0 278 752, for example Polyoxyethylenethertenside.
  • the amount of wetting agent is preferably 1 to 20 g / l.
  • the invention thus relates to aqueous pickling activation solutions for the pretreatment of aluminum-steel composite materials in front of an acidic dip tinning bath, which is characterized are that they are sulfuric acid, hexafluorosilicic acid, Wetting agents, subgroup metal cations and nitrate and / or Contain nitrite ions, in particular consist of them and prepare the substrate surface in such a way that uniform, adhesive tinning is obtained.
  • the Amount of subgroup metal cations, in particular from the Group 1 and 2 and 5 to 8 of the Periodic Table of the Elements is preferably 0.05 to 1% by weight.
  • the amount of nitrite ions is preferably 0.05 to 3% by weight, while the amount of nitrate ions is preferably in the same Area.
  • Another embodiment of the invention includes a method for pickling activation of aluminum-steel composite materials, the is characterized in that pickling activation solutions with the composite at temperatures in the range of 15 to 70 ° C in Contact in the course of 1 to 9 min.
  • test pieces were used as test pieces used. These are half shells made of steel, which on the inside with an aluminum alloy (approx. 80-90% aluminum, alloyed essentially with tin and silicon) are.
  • aluminum alloy approximately 80-90% aluminum, alloyed essentially with tin and silicon
  • the substrates were degreased in a manner known per se and rinsed.
  • the substrates were placed in the solution for 5 minutes dipped.
  • the temperature of the pickling solution was 40 ° C. After The substrates were rinsed for one minute during activation.
  • the substrates of Examples 1 to 3 and the Comparative Example were each placed in a commercially available, acidic, external electroless plating tinning bath analogous to example 1 to 3 and the comparative example. It was at 30-40 ° C worked.
  • the pickling with the nitric acid pretreatment caused a strong attack on the iron surfaces.
  • the following dip tinning with dip tinning bath 1, 2 or 3 resulted in uneven tin deposits on the substrate surfaces.
  • the iron surface had no closed tin surface.
  • the adhesive strength was checked as above.
  • the adhesive film test showed significant tin detachment from the aluminum surface.
  • the tin layer thickness on the aluminum alloy was 1.8 to 4.2 ⁇ m before the test and only 0.2 to 0.5 ⁇ m after the test.
  • Tinning bath 1 Tinning bath 2 Tinning bath 3 Solution 1 very good tin deposition, excellent adhesion very good tin deposition, excellent adhesion good tin deposition, very good adhesion Solution 2 very good tin separation, very good adhesion very good tin separation, very good adhesion good tin deposition, very good adhesion Solution 3 very good tin separation, very good adhesion very good tin separation, very good adhesion good tin deposition, very good adhesion Comparative example uneven tin deposition, low adhesive strength uneven tin deposition, low adhesive strength very uneven tin deposition, low adhesive strength very uneven tin deposition, low adhesive strength

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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)
  • Inorganic Chemistry (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Chemically Coating (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Coating With Molten Metal (AREA)

Abstract

The invention relates to an aqueous preparation for the pickling and activation of aluminum-steel composites prior to electroless dip tinning. Specifically, the invention provides pickling/activation solutions for the pretreatment of aluminum-steel composites prior to dip tinning which comprise sulfuric acid, hexafluorosilicic acid, at least one wetting agent, at least one transition metal cation and nitrate and/or nitrite ions.

Description

Die Erfindung betrifft eine wäßrige Zubereitung für die Beizung und Aktivierung von Aluminium-Stahl-Verbundwerkstoffen vor einer außenstromlosen Tauchverzinnung. Beispiele für Aluminium-Stahl-Verbundwerkstoffe sind Gleitlager, Buchsen, Anlaufscheiben, Trockengleitlager usw. für Pumpen, Motoren und Getriebe. Nach der Beizaktivierung werden auf den Aluminium- und Stahloberflächen des Substrates bei einer anschließenden Tauchverzinnung gleichmäßige, besonders haftfeste Zinnüberzüge erzielt.The invention relates to an aqueous preparation for pickling and activation of aluminum-steel composites before one electroless plating. Examples of aluminum-steel composite materials are plain bearings, bushings, thrust washers, Dry sliding bearings etc. for pumps, motors and gears. After pickling activation, the aluminum and Steel surfaces of the substrate during a subsequent dip tinning even, particularly adhesive tin coatings achieved.

Aus EP-A-0 278 752 ist bekannt, Substrate aus reinen Aluminiumlegierungen und auch Aluminium-Stahl-Verbundmetalle nach einer Vorbehandlung, bestehend aus Entfettung und Beizung, mit sauren Zinnsalzelektrolyten im Austauschverfahren zu verzinnen.EP-A-0 278 752 discloses substrates made of pure aluminum alloys and also aluminum-steel composite metals after one Pretreatment consisting of degreasing and pickling with acid Tin tin electrolytes in an exchange process.

Die DE-A-29 17 019 beschreibt ein Verfahren zur Metallisierung von Aluminium-Stahl-Verbundmaterial. Das dabei verwendete Bad besteht aus einer Mineralsäure, einer Quelle für Fluoridionen, fluoridhaltige Ionen oder deren Gemische, und einer Quelle für Zinn(II)ionen in einer Konzentration von ungefähr 1 bis 75 g/l. Vorher wird das Verbundmaterial mit einer Fluoridionen enthaltenden Mineralsäure aktiviert.DE-A-29 17 019 describes a method for metallization of aluminum-steel composite material. The used here Bath consists of a mineral acid, a source of fluoride ions, fluoride-containing ions or their mixtures, and a source for stannous ions in a concentration of approximately 1 to 75 g / l. Before the composite material with a mineral acid containing fluoride ions activated.

Weiter ist aus der US-A-5 227 016 bekannt, Aluminiumoberflächen mit einem Bad der Zusammensetzung

  • (A) eine oxydierende anorganische Säure
  • (B) Phosphorsäure
  • (C) Schwefelsäure
  • (D) eine Fluoridionenquelle
  • (E) eine Quelle für komplexe Fluoridione, vorzugsweise Hexafluorokieselsäure
  • (F) eine organische Carbonsäure mit 1-10 Kohlenstoffatomen und
  • (G) eine Quelle für vierwertiges Mangan
    • zu oxydieren.Furthermore, it is known from US-A-5 227 016 aluminum surfaces with a bath of the composition
  • (A) an oxidizing inorganic acid
  • (B) phosphoric acid
  • (C) sulfuric acid
  • (D) a source of fluoride ions
  • (E) a source of complex fluoride ions, preferably hexafluorosilicic acid
  • (F) an organic carboxylic acid with 1-10 carbon atoms and
  • (G) a source of tetravalent manganese
    • to oxidize.

    Die bekannten Systeme aus Entfettung, Beize und Verzinnung, zeigen, angewandt auf Substrate aus Aluminium-Stahl-Verbundwerkstoffen unzureichende Ergebnisse:

    • die Reinigung, Beizung und Verzinnung der Stahloberflächen und der Aluminiumoberflächen erfolgt ungleichmäßig,
    • die Zinnabscheidung auf den Stahloberflächen erfolgt ungleichmäßig und ergibt keine geschlossene Oberfläche,
    • die Haftfestigkeit der auf dem Aluminium abgeschiedenen Zinnschicht ist unzureichend.
    The known systems from degreasing, pickling and tinning show insufficient results when applied to substrates made of aluminum-steel composite materials:
    • the cleaning, pickling and tinning of the steel surfaces and the aluminum surfaces is uneven,
    • the tin deposition on the steel surfaces is uneven and does not result in a closed surface,
    • the adhesive strength of the tin layer deposited on the aluminum is insufficient.

    Die vorliegende Erfindung befaßt sich deshalb mit dem technischen Problem, die Vorbehandlung des Aluminium-Stahl-Verbundwerkstoffes zu optimieren. Insbesondere besteht die Aufgabe der vorliegenden Erfindung darin, bei Anwendung der bekannten Tauchverzinnungsbäder gleichmäßige, haftfeste Zinnüberzüge sowohl auf den Aluminium- als auch auf den Stahloberflächen des Substrats herzustellen.The present invention is therefore concerned with the technical Problem, the pretreatment of the aluminum-steel composite to optimize. In particular, the task of present invention therein, using the known Dip tinning baths uniform, adhesive tin coatings both on the aluminum as well as on the steel surfaces of the Manufacture substrate.

    Das vorgenannte Problem wird erfindungsgemäß gelöst, indem für die Vorbehandlung des Substrats eine neue Beizaktivierung verwendet wird, die folgende Komponenten und Zusätze enthält:

    • Schwefelsäure zur Beizung der Stahloberflächen,
    • Hexafluorokieselsäure zur Beizung der Aluminiumoberflächen,
    • Tenside zur gleichmäßigen Benetzung der Substratoberflächen mit der Lösung,
    • Nebengruppenmetallkationen zur Optimierung der Beizung und Aktivierung der Aluminiumoberfläche,
    The aforementioned problem is solved according to the invention by using a new pickling activation for the pretreatment of the substrate which contains the following components and additives:
    • Sulfuric acid for pickling the steel surfaces,
    • Hexafluorosilicic acid for pickling the aluminum surfaces,
    • Surfactants for uniform wetting of the substrate surfaces with the solution,
    • Subgroup metal cations to optimize the pickling and activation of the aluminum surface,

    Bei Versuchen zur Beizvorbehandlung von Aluminium-Stahl-Verbundwerkstoffen wurde gefunden, daß eine Beizaktivierung enthaltend Schwefelsäure und Hexafluorokieselsäure (wobei die Gehalte der beiden Mineralsäuren jeweils einer der beiden Substratlegierungen angepaßt sind) deutlich besser wirksam war als andere Vorbehandlungen. Der Gehalt an Schwefelsäure beträgt daher vorzugsweise 50 bis 150 g/l. Der Gehalt an Hexafluorokieselsäure beträgt daher vorzugsweise 5 bis 25 g/l.In attempts to pre-pickle aluminum-steel composites it was found to contain a pickling activation Sulfuric acid and hexafluorosilicic acid (the contents of the two mineral acids each one of the two substrate alloys adapted) was significantly more effective than other pretreatments. The sulfuric acid content is therefore preferably 50 to 150 g / l. The content of hexafluorosilicic acid is therefore preferably 5 to 25 g / l.

    Verdünnte Schwefelsäure eignet sich zur Beizung von Eisenlegierungen, bewirkt aber, bei Temperaturen von bis zu 70°C und Tauchzeiten von wenigen Minuten, keinen merklichen Angriff auf Aluminium. Hexafluorokieselsäure reinigt und aktiviert Aluminiumlegierungen, ohne Eisenoberflächen signifikant anzugreifen. Die Kombination beider Säuren wird der komplexen Substratstruktur aus zwei Legierungen mit stark unterschiedlichen chemischen und physikalischen Eigenschaften gerecht. Beispiele für Aluminium-Stahl-Verbundwerkstoffe sind Gleitlager, Buchsen, Anlaufscheiben, Trockengleitlager usw. für Pumpen, Motoren und Getriebe.Dilute sulfuric acid is suitable for pickling iron alloys, causes, however, at temperatures of up to 70 ° C and Diving times of a few minutes, no noticeable attack on Aluminum. Hexafluorosilicic acid cleans and activates aluminum alloys, without significantly attacking iron surfaces. The combination of both acids becomes the complex substrate structure made of two alloys with very different chemical and physical properties. Examples of aluminum-steel composite materials are plain bearings, bushings, thrust washers, Dry sliding bearings etc. for pumps, motors and gears.

    Um im folgenden sauren, außenstromlosen Tauchverzinnungsbad eine gleichmäßige und haftfeste Zinnabscheidung zu erreichen, müssen dieser Beizaktivierung aber noch weitere geeignete Additive zugefügt werden.To the following acidic, electroless plating tin bath to achieve an even and adherent tin deposition, However, this pickling activation also needs other suitable additives be added.

    Zur weiteren Optimierung der Beizwirkung und insbesondere zur weitergehenden Aktivierung der Aluminiumoberflächen des Substrats müssen der Säuremischung aber noch Nebengruppenmetallkationen, wie z. B. Mangan(II)-, Nickel(II)-, Eisen(III)-Ionen, in Konzentrationen von 0,05 bis 1 Gew.-% zuzugeben werden. Besonders vorteilhaft sind Mangan(II)-Ionen in einer Konzentration von 0,1 Gew.-% bei einer Beiztemperatur von 40°C und Beizzeiten von 5 Minuten. For further optimization of the pickling effect and in particular for further activation of the aluminum surfaces of the substrate but still need the acid mixture Subgroup metal cations such. B. manganese (II) -, nickel (II) -, Iron (III) ions, in concentrations of 0.05 to 1% by weight will be admitted. Manganese (II) ions in one are particularly advantageous Concentration of 0.1% by weight at a pickling temperature of 40 ° C and pickling times of 5 minutes.

    Weiterhin hat sich die Zugabe von Nitrat- und/oder Nitritionen als positiv erwiesen. Zusätze von Alkalimetallnitrat- und Alkalimetallnitritsalzen, wie Natriumnitrat, Kaliumnitrat, Natriumnitrit oder Kaliumnitrit in Konzentrationen von 0,05 bis 3 Gew.-%, wobei eine Zugabe von 0,5 Gew.-% Kaliumnitrat optimal ist, verbessern die Beiz- und Reinigungsergebnisse der Beizaktivierungslösung deutlich.Furthermore, the addition of nitrate and / or nitrite ions proven positive. Additions of alkali metal nitrate and alkali metal nitrite salts, such as sodium nitrate, potassium nitrate, sodium nitrite or potassium nitrite in concentrations from 0.05 to 3 wt .-%, with an addition of 0.5 wt .-% potassium nitrate optimal improve the pickling and cleaning results of the pickling activation solution clear.

    Zur Erzielung einer gleichmäßigen Beizaktivierung ist außerdem eine gleichmäßige Oberflächenbenetzung erforderlich, die durch Zugabe von Netzmitteln erreicht wird. Geeignet sind grundsätzlich alle das Substrat gut benetzenden Tenside, welche eine ausreichende chemische Beständigkeit in dem Beizaktivierungselektrolyten besitzen. Besonders geeignet sind Netzmittel, wie sie in Tauchverzinnungsbädern angewendet werden, die in EP-A-0 278 752 offenbart sind, beispielsweise Polyoxyethylenethertenside. Die Menge der Netzmittel beträgt vorzugsweise 1 bis 20 g/l.To achieve even pickling activation is also uniform surface wetting required by Addition of wetting agents is achieved. Basically, are suitable all surfactants well wetting the substrate, which have a sufficient chemical resistance in the pickling activation electrolyte have. Wetting agents such as they are used in immersion tinning baths which are used in EP-A-0 278 752, for example Polyoxyethylenethertenside. The amount of wetting agent is preferably 1 to 20 g / l.

    Gegenstand der Erfindung sind somit wäßrige Beizaktivierungslösungen für die Vorbehandlung von Aluminium-Stahl-Verbundwerkstoffen vor einem sauren Tauchverzinnungsbad, die dadurch gekennzeichnet sind, daß sie Schwefelsäure, Hexafluorokieselsäure, Netzmittel, Nebengruppenmetallkationen und Nitratund/oder Nitrit-Ionen enthalten, insbesondere daraus bestehen und die Substratoberfläche derart vorbereiten, daß im Anschluß eine gleichmäßige, haftfeste Verzinnung erhalten wird. Die Menge der Nebengruppenmetallkationen, die insbesondere aus der Gruppe 1 und 2 sowie 5 bis 8 des Periodensystems der Elemente ausgewählt sind, beträgt vorzugsweise 0,05 bis 1 Gew.-%. Die Menge an Nitritionen beträgt vorzugsweise 0,05 bis 3 Gew.-%, während die Menge der Nitrationen vorzugsweise in dem gleichen Bereich liegt.The invention thus relates to aqueous pickling activation solutions for the pretreatment of aluminum-steel composite materials in front of an acidic dip tinning bath, which is characterized are that they are sulfuric acid, hexafluorosilicic acid, Wetting agents, subgroup metal cations and nitrate and / or Contain nitrite ions, in particular consist of them and prepare the substrate surface in such a way that uniform, adhesive tinning is obtained. The Amount of subgroup metal cations, in particular from the Group 1 and 2 and 5 to 8 of the Periodic Table of the Elements is preferably 0.05 to 1% by weight. The The amount of nitrite ions is preferably 0.05 to 3% by weight, while the amount of nitrate ions is preferably in the same Area.

    Ein weitere Ausführungsform der Erfindung umfaßt ein Verfahren zur Beizaktivierung von Aluminium-Stahl-Verbundwerkstoffen, das dadurch gekennzeichnet ist, daß man Beizaktivierungslösungen mit dem Verbund bei Temperaturen im Bereich von 15 bis 70°C im Verlauf von 1 bis 9 min in Kontakt bringt.Another embodiment of the invention includes a method for pickling activation of aluminum-steel composite materials, the is characterized in that pickling activation solutions with the composite at temperatures in the range of 15 to 70 ° C in Contact in the course of 1 to 9 min.

    Ausfühungsbeispiele:Ausfühungsbeispiele: Beispiel 1:Example 1: Substratesubstrates

    Als Probestücke wurden handelsübliche Aluminium-Stahl-Verbundlager verwendet. Dies sind Halbschalen aus Stahl, welche auf der Innenseite mit einer Aluminiumlegierung (ca. 80-90% Aluminium, legiert im wesentlichen mit Zinn und Silicium) walzplattiert sind.Commercial aluminum-steel composite bearings were used as test pieces used. These are half shells made of steel, which on the inside with an aluminum alloy (approx. 80-90% aluminum, alloyed essentially with tin and silicon) are.

    Entfettungdegreasing

    Die Substrate wurden in an sich bekannter Weise entfettet und gespült.The substrates were degreased in a manner known per se and rinsed.

    Beizaktivierungpickling and activation

    Die Substrate wurden für die Dauer von 5 Minuten in die Lösung getaucht. Die Temperatur der Beizlösung betrug 40°C. Nach der Aktivierung wurden die Substrate eine Minute gespült.The substrates were placed in the solution for 5 minutes dipped. The temperature of the pickling solution was 40 ° C. After The substrates were rinsed for one minute during activation.

    Lösung 1Solution 1

  • 100 g/l H2SO4 100 g / l H 2 SO 4
  • 20 g/l H2SiF6 20 g / l H 2 SiF 6
  • 10 g/l Polyoxyethylenether des Decylalkohols mit 5 Oxyethyleneinheiten10 g / l polyoxyethylene ether of decyl alcohol with 5 oxyethylene units
  • 5 g/l KNO3 5 g / l KNO 3
  • 1 g/l MnSO4*1 H2O1 g / l MnSO 4 * 1 H 2 O

    • Beispiel 2:Example 2: Lösung 2Solution 2

  • 100 g/l H2SO4 100 g / l H 2 SO 4
  • 20 g/l H2SiF6 20 g / l H 2 SiF 6
  • 10 g/l Polyoxyethylenether des Hexylalkoholsilans (CH3)3Si(CH2)6OH mit 4 Oxyethyleneinheiten10 g / l polyoxyethylene ether of hexyl alcohol silane (CH 3 ) 3 Si (CH 2 ) 6 OH with 4 oxyethylene units
  • 5 g/l NaNO2 5 g / l NaNO 2
  • 1 g/l NiSO4*6 H2O1 g / l NiSO 4 * 6 H 2 O

    • Beispiel 3:Example 3: Lösung 3Solution 3

  • 100 g/l H2SO4 100 g / l H 2 SO 4
  • 20 g/l H2SiF6 20 g / l H 2 SiF 6
  • 10 g/l Polyoxyethylenether des Decylalkohols mit 5 Oxyethyleneinheiten10 g / l polyoxyethylene ether of decyl alcohol with 5 oxyethylene units
  • 5 g/l NaNO3 5 g / l NaNO 3
  • 3 g/l Fe2(SO4)3*x H2O3 g / l Fe 2 (SO 4 ) 3 * x H 2 O

    • Vergleichsbeispiel:Comparative Example:

  • 120 g/l HNO3 120 g / l ENT 3
  • 20 g/l H2SiF6 20 g / l H 2 SiF 6
  • 5 g/l Polyoxyethylenether des Stearylalkohols mit 20 Oxyethyleneinheiten5 g / l polyoxyethylene ether of stearyl alcohol with 20 oxyethylene units
  • 2 g/l Gelatine2 g / l gelatin

    • Beispiel 4:Example 4: Verzinnungtinning

    Die Substrate der Beispiele 1 bis 3 und des Vergleichsbeispiels wurden jeweils für die Dauer von 5 Minuten in ein handelübliches, saures, außenstromloses Tauchverzinnungsbad analog Beispiel 1 bis 3 und dem Vergleichsbeispiel getaucht. Es wurde bei 30-40°C gearbeitet.The substrates of Examples 1 to 3 and the Comparative Example were each placed in a commercially available, acidic, external electroless plating tinning bath analogous to example 1 to 3 and the comparative example. It was at 30-40 ° C worked.

    Tauchverzinnungsbad 1Dip tinning bath 1

  • 100 g/l H2SO4 100 g / l H 2 SO 4
  • 40 g/l SnSO4 40 g / l SnSO 4
  • 3,5 g/l HBF4 3.5 g / l HBF 4
  • 2 g/l Gelatine2 g / l gelatin
  • 1 g/l Polyoxyethylenether des Decylalkohols mit 5 Oxyethyleneinheiten1 g / l polyoxyethylene ether of decyl alcohol with 5 oxyethylene units

    • Tauchverzinnungsbad 2Dip tinning bath 2

  • 100 g/l H2SO4 100 g / l H 2 SO 4
  • 40 g/l SnSO4 40 g / l SnSO 4
  • 7 g/l KBF4 7 g / l KBF 4
  • 2 g/l Gelatine2 g / l gelatin
  • 0,1 g/l Polyoxyethylenether des Stearylalkohols mit 20 Oxyethyleneinheiten0.1 g / l polyoxyethylene ether of stearyl alcohol with 20 oxyethylene units

    • Tauchverzinnungsbad 3Dip tinning bath 3

  • 100 g/l CH3SO3H100 g / l CH 3 SO 3 H
  • 30 g/l (CH3SO3)2Sn30 g / l (CH 3 SO 3 ) 2 Sn
  • 2 g/l H2SiF6 2 g / l H 2 SiF 6
  • 1 g/l Gelatine1 g / l gelatin
  • 0,1 g/l Polyoxyethylenether des Hexylalkoholsilans (CH3)3Si(CH2)6OH mit 4 Oxyethyleneinheiten0.1 g / l polyoxyethylene ether of hexyl alcohol silane (CH 3 ) 3 Si (CH 2 ) 6 OH with 4 oxyethylene units

    • VerzinnungsergebnisseVerzinnungsergebnisse

    Nach einer Beizaktivierung mit Lösung 1, Lösung 2 oder Lösung 3 wurden mit einem Tauchverzinnungsbad 1, 2 oder 3 gleichmäßige, glatte, geschlossene und sehr haftfeste Zinnschichten auf Stahl- und Aluminiumoberflächen abgeschieden. Die Schichtdicken des Zinnüberzugs betrugen 1,8 bis 4,2 µm auf Aluminium- und 0,4 bis 0,8 µm auf den Stahlflächen. Zur Kontrolle der Haftfestigkeit wurde auf die verzinnten Substratoberflächen ein transparenter Klebefilmstreifen (Tesa®) aufgeklebt und unter Zuhilfenahme eines Bleistifts so fest wie möglich angedrückt und ruckartig unter einem Winkel von 45° abgerissen. In allen drei Fällen wurde kein Zinn abgelöst. Die Zinnschichten nach dem Test betrugen wiederum 1,8 bis 4,2 µm auf Aluminium- und 0,4 bis 0,8 µm auf den Stahloberflächen.After pickling activation with solution 1, solution 2 or solution 3 1, 2 or 3 uniform, smooth, closed and very adhesive tin layers Steel and aluminum surfaces deposited. The layer thicknesses the tin coating was 1.8 to 4.2 µm on aluminum and 0.4 up to 0.8 µm on the steel surfaces. To control the adhesive strength became a transparent one on the tinned substrate surfaces Adhesive film strips (Tesa®) glued on and with the help of a pencil pressed as tightly as possible and jerky Torn off at an angle of 45 °. In all three cases no tin was peeled off. The tin layers after the test were again 1.8 to 4.2 µm on aluminum and 0.4 to 0.8 µm on the steel surfaces.

    Vergleichsbeispiel:Comparative Example:

    Die Beizung mit der salpetersauren Vorbehandlung bewirkte einen starken Angriff auf die Eisenflächen. Die folgende Tauchverzinnung mit Tauchverzinnungsbad 1, 2 oder 3 ergab ungleichmäßige Zinnabscheidungen auf den Substratoberflächen. Die Eisenoberfläche wies keine geschlossene Zinnoberfläche auf. Die Kontrolle der Haftfestigkeit erfolgte wie oben. Der Klebefilm-Test ergab deutliche Zinnablösungen von der Aluminiumoberfläche. Die Zinnschichtdicke auf der Aluminiumlegierung betrug vor dem Test 1,8 bis 4,2 µm und nach dem Test nur 0,2 bis 0,5 µm. Verzinnungsbad 1 Verzinnungsbad 2 Verzinnungsbad 3 Lösung 1 sehr gute Zinnabscheidung, hervorragende Haftung sehr gute Zinnabscheidung, hervorragende Haftung gute Zinnabscheidung, sehr gute Haftung Lösung 2 sehr gute Zinnabscheidung, sehr gute Haftung sehr gute Zinnabscheidung, sehr gute Haftung gute Zinnabscheidung, sehr gute Haftung Lösung 3 sehr gute Zinnabscheidung, sehr gute Haftung sehr gute Zinnabscheidung, sehr gute Haftung gute Zinnabscheidung, sehr gute Haftung Vergleichsbeispiel ungleichmäßige Zinnabscheidung, geringe Haftfestigkeit ungleichmäßige Zinnabscheidung, geringe Haftfestigkeit sehr ungleichmäßige Zinnabscheidung,geringe Haftfestigkeit The pickling with the nitric acid pretreatment caused a strong attack on the iron surfaces. The following dip tinning with dip tinning bath 1, 2 or 3 resulted in uneven tin deposits on the substrate surfaces. The iron surface had no closed tin surface. The adhesive strength was checked as above. The adhesive film test showed significant tin detachment from the aluminum surface. The tin layer thickness on the aluminum alloy was 1.8 to 4.2 µm before the test and only 0.2 to 0.5 µm after the test. Tinning bath 1 Tinning bath 2 Tinning bath 3 Solution 1 very good tin deposition, excellent adhesion very good tin deposition, excellent adhesion good tin deposition, very good adhesion Solution 2 very good tin separation, very good adhesion very good tin separation, very good adhesion good tin deposition, very good adhesion Solution 3 very good tin separation, very good adhesion very good tin separation, very good adhesion good tin deposition, very good adhesion Comparative example uneven tin deposition, low adhesive strength uneven tin deposition, low adhesive strength very uneven tin deposition, low adhesive strength

    Claims (11)

    1. Pickling/activation solutions for the pretreatment of aluminium-steel composites prior to dip tinning, characterized in that they comprise sulphuric acid, hexafluorosilicic acid, wetting agents and transition metal cations.
    2. Solutions according to Claim 1, characterized in that the sulphuric acid content is from 50 to 150 g/l.
    3. Solutions according to Claim 1, characterized in that the hexafluorosilicic acid content is from 5 to 25 g/l.
    4. Solutions according to Claim 1, characterized in that the wetting agent content is from 1 to 20 g/l.
    5. Solutions according to Claim 1, characterized in that the wetting agents are selected from the group consisting of polyoxyethylene ether surfactants.
    6. Solutions according to Claim 1, characterized in that the transition metal cation content is from 0.05 to 1% by weight.
    7. Solutions according to Claim 1, characterized in that the transition metal cations are selected from transition groups I and II and V to VIII.
    8. Solutions according to Claim 1, characterized in that they comprise nitrate and/or nitrite ions.
    9. Solutions according to Claim 8, characterized in that the nitrite ion content is from 0.05 to 3% by weight.
    10. Solutions according to Claim 1, characterized in that the nitrate ion content is from 0.05 to 3% by weight.
    11. Process for the pickling and activation of aluminium-steel composites prior to dip tinning, characterized in that it comprises bringing pickling/activation solutions according to one or more of Claims 1 to 10 into contact with the composite for from 1 to 9 minutes and at temperatures in the range from 15 to 70°C.
    EP99111464A 1998-06-27 1999-06-12 Pickling-activating solution for pre-treatment of aluminium-steel composites before electroless tin plating Expired - Lifetime EP0967301B1 (en)

    Applications Claiming Priority (3)

    Application Number Priority Date Filing Date Title
    DE19828811 1998-06-27
    DE19828811A DE19828811C1 (en) 1998-06-27 1998-06-27 Mordant activation solution for aluminum-steel compound material to be tin-plated
    US09/340,004 US6194369B1 (en) 1998-06-27 1999-06-25 Pickling/activation solution for the pretreatment of aluminum-steel composites prior to dip tinning

    Publications (3)

    Publication Number Publication Date
    EP0967301A2 EP0967301A2 (en) 1999-12-29
    EP0967301A3 EP0967301A3 (en) 2000-06-28
    EP0967301B1 true EP0967301B1 (en) 2003-11-19

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    US (1) US6194369B1 (en)
    EP (1) EP0967301B1 (en)
    AT (1) ATE254678T1 (en)
    CA (1) CA2276475C (en)
    DE (2) DE19828811C1 (en)
    ES (1) ES2210902T3 (en)
    PT (1) PT967301E (en)

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    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US6436816B1 (en) * 1998-07-31 2002-08-20 Industrial Technology Research Institute Method of electroless plating copper on nitride barrier
    US8192556B2 (en) 2002-10-15 2012-06-05 Henkel Kgaa Pickling or brightening/passivating solution and process for steel and stainless steel
    US10443135B1 (en) * 2018-05-11 2019-10-15 Macdermid Enthone Inc. Near neutral pH pickle on multi-metals
    CN111676474A (en) * 2020-06-05 2020-09-18 贵州水钢同鑫晟金属制品有限公司 Activating agent for low-temperature rapid phosphorization of prestressed steel strand and preparation method thereof
    CN113445092B (en) * 2021-06-29 2022-10-11 钢铁研究总院 Copper plating method for 0Cr15Ni25Ti2MoAlVB stainless steel surface

    Family Cites Families (7)

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    Publication number Priority date Publication date Assignee Title
    JPS5629751B2 (en) * 1973-05-22 1981-07-10
    US4170525A (en) * 1978-04-28 1979-10-09 Gould Inc. Process for plating a composite structure
    US4192722A (en) * 1978-07-25 1980-03-11 Reynolds Metals Company Composition and method for stannate plating of large aluminum parts
    IL81530A0 (en) * 1987-02-10 1987-09-16 Techno Chemica Ltd Tin coating immersion solution and coating process using the same
    US5227016A (en) * 1992-02-25 1993-07-13 Henkel Corporation Process and composition for desmutting surfaces of aluminum and its alloys
    JP3195144B2 (en) * 1993-11-05 2001-08-06 新日本製鐵株式会社 Highly efficient pickling method for Cr-containing steel
    IT1276955B1 (en) * 1995-10-18 1997-11-03 Novamax Itb S R L PICKLING AND PASSIVATION PROCESS OF STAINLESS STEEL WITHOUT THE USE OF NITRIC ACID

    Also Published As

    Publication number Publication date
    EP0967301A3 (en) 2000-06-28
    DE19828811C1 (en) 1999-12-09
    DE59907772D1 (en) 2003-12-24
    ATE254678T1 (en) 2003-12-15
    PT967301E (en) 2004-04-30
    US6194369B1 (en) 2001-02-27
    ES2210902T3 (en) 2004-07-01
    CA2276475A1 (en) 1999-12-27
    EP0967301A2 (en) 1999-12-29
    CA2276475C (en) 2007-05-22

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