EP0967301A2 - 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
EP0967301A2
EP0967301A2 EP99111464A EP99111464A EP0967301A2 EP 0967301 A2 EP0967301 A2 EP 0967301A2 EP 99111464 A EP99111464 A EP 99111464A EP 99111464 A EP99111464 A EP 99111464A EP 0967301 A2 EP0967301 A2 EP 0967301A2
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Prior art keywords
pickling
aluminum
solutions according
activation
tin
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EP99111464A
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German (de)
French (fr)
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EP0967301B1 (en
EP0967301A3 (en
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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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    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (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 composites 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 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 after pretreatment consisting of degreasing and pickling, with acidic tin salt electrolytes in the exchange process to tin.

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 inadequate 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,
  • Nitrat- und/oder Nitrit-Ionen 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 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,
  • Nitrate and / or nitrite ions 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 composites 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.In the following acidic, electroless plating tin bath to achieve an even and adherent tin deposit, However, this pickling activation must also contain 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.-% zugegeben 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 the acid mixture still have subgroup metal cations, such as B. manganese (II), nickel (II), iron (III) ions, in concentrations of 0.05 to 1 wt .-% are added. Especially Manganese (II) ions in a concentration are advantageous 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 Polyoxyethylene ether surfactants. 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 Nitrat-und/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 composites 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:Design examples: 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.Commercially available 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.

BeizaktivierungStain 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 submerged. 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 placed in a commercially available, acidic, external electroless 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 3Dipping tin 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

    • VerzinnungsergebnisseTinning results

    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 microns 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,ger inge 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 deposition, very good adhesion very good tin deposition, very good adhesion good tin deposition, very good adhesion Solution 3 very good tin deposition, very good adhesion very good tin deposition, 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 (10)

    Beizaktivierungslösungen für die Vorbehandlung von Aluminium-Stahl-Verbundwerkstoffen vor einer Tauchverzinnung, dadurch gekennzeichnet, daß sie Schwefelsäure, Hexafluorokieselsäure, Netzmittel, Nebengruppenmetallkationen und Nitrat-und/oder Nitrit-Ionen enthalten.Pickling activation solutions for the pretreatment of aluminum-steel composites before a dip tinning, thereby characterized that they contain sulfuric acid, hexafluorosilicic acid, Wetting agents, subgroup metal cations and nitrate and / or Contain nitrite ions. Lösungen nach Anspruch 1, dadurch gekennzeichnet, daß der Gehalt an Schwefelsäure 50 bis 150 g/l beträgtSolutions according to claim 1, characterized in that the Sulfuric acid content is 50 to 150 g / l Lösungen nach Anspruch 1, dadurch gekennzeichnet, daß der Gehalt an Hexafluorokieselsäure 5 bis 25 g/l beträgt.Solutions according to claim 1, characterized in that the Hexafluorosilicic acid content is 5 to 25 g / l. Lösungen nach Anspruch 1, dadurch gekennzeichnet, daß der Gehalt an Netzmittel 1 bis 20 g/l beträgt.Solutions according to claim 1, characterized in that the Wetting agent content is 1 to 20 g / l. Lösungen nach Anspruch 1, dadurch gekennzeichnet, daß die Netzmittel ausgewählt sind aus Polyoxyethylenethertensiden.Solutions according to claim 1, characterized in that the Wetting agents are selected from polyoxyethylene ether surfactants. Lösungen nach Anspruch 1, dadurch gekennzeichnet, daß der Gehalt an Nebengruppenmetallkationen 0,05 bis 1 Gew.-% beträgt.Solutions according to claim 1, characterized in that the Content of subgroup metal cations is 0.05 to 1 wt .-%. Lösungen nach Anspruch 1, dadurch gekennzeichnet, daß die Nebengruppenmetallkationen ausgewählt sind aus den Nebengruppen 1 bis 2 und 5 bis 8.Solutions according to claim 1, characterized in that the Subgroup metal cations are selected from the subgroups 1 to 2 and 5 to 8. Lösungen nach Anspruch 1, dadurch gekennzeichnet, daß der Gehalt an Nitritionen 0,05 bis 3 Gew.-% beträgt.Solutions according to claim 1, characterized in that the The nitrite ion content is 0.05 to 3% by weight. Lösungen nach Anspruch 1, dadurch gekennzeichnet, daß der Gehalt an Nitrationen 0,05 bis 3 Gew.-% beträgt. Solutions according to claim 1, characterized in that the The nitrate ion content is 0.05 to 3% by weight. Verfahren zur Beizaktivierung von Aluminum-Stahl-Verbundwerkstoffen, dadurch gekennzeichnet, daß man Beizaktivierungslösungen gemäß einem oder mehreren der Ansprüche 1 bis 9 mit dem Verbund bei Temperaturen im Bereich von 15 bis 70 °C im Verlauf von 1 bis 9 min mit in Kontakt bringt.Process for pickling activation of aluminum-steel composites, characterized in that pickling activation solutions according to one or more of claims 1 to 9 with the composite at temperatures in the range of 15 to 70 ° C in the course of 1 to 9 min.
    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)

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    DE19828811A DE19828811C1 (en) 1998-06-27 1998-06-27 Mordant activation solution for aluminum-steel compound material to be tin-plated
    DE19828811 1998-06-27
    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

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    EP0967301A2 true EP0967301A2 (en) 1999-12-29
    EP0967301A3 EP0967301A3 (en) 2000-06-28
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    AT (1) ATE254678T1 (en)
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    US6436816B1 (en) * 1998-07-31 2002-08-20 Industrial Technology Research Institute Method of electroless plating copper on nitride barrier
    KR100777171B1 (en) * 2002-10-15 2007-11-16 헨켈 코만디트게젤샤프트 아우프 악티엔 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

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

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