EP0328128B1 - Process concerning the adhesion between metallic materials and galvanic aluminium layers and the non-aqueous electrolyte used therein - Google Patents

Process concerning the adhesion between metallic materials and galvanic aluminium layers and the non-aqueous electrolyte used therein Download PDF

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EP0328128B1
EP0328128B1 EP89102319A EP89102319A EP0328128B1 EP 0328128 B1 EP0328128 B1 EP 0328128B1 EP 89102319 A EP89102319 A EP 89102319A EP 89102319 A EP89102319 A EP 89102319A EP 0328128 B1 EP0328128 B1 EP 0328128B1
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metal
anhydrous
nickel
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EP0328128A1 (en
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Herbert Prof. Dr. Lehmkuhl
Klaus-Dieter Mehler
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Studiengesellschaft Kohle gGmbH
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance

Definitions

  • the invention relates to methods for the metal coating of metal materials, in particular of low-alloy, high-strength steels.
  • the invention also relates to the non-aqueous electrolytes used in the above process.
  • Certain metals such as copper, can be directly electroplated with aluminum after appropriate mechanical and / or chemical pretreatments to remove fat and / or oxide layers from the surface of the workpieces.
  • metals such as, for example, iron materials and in particular special steels, generally no adhesive layers of galvanoaluminium can be obtained in the same way.
  • DE-PS 22 60 191 (Siemens AG, priority: 08.12.1972) describes such a method, which is characterized in that at least the last process step, which is used to shape the workpieces, is carried out under an aprotic, water- and oxygen-free protective medium. In the examples, milling, sawing or sanding are mentioned as the last shaping process step.
  • a decisive disadvantage of the two last-mentioned procedures is that during the electrodeposition of the metals serving as adhesion promoters, co-separation of hydrogen cannot be avoided.
  • Low-alloy high-strength steels for example as shown in Table 1, are very sensitive to embrittlement to hydrogen. Aqueous electrolyte solutions are therefore unsuitable for coating such steels.
  • DE-A-2012846 discloses non-aqueous, DMSO-containing solutions of metal salts for electroplating without hydrogen fragility.
  • the invention consequently relates to methods for the metal coating of metal materials, in particular low-alloy high-strength steels, galvanic adhesion-promoting layers of iron, iron and nickel, nickel, cobalt, copper or alloys of the abovementioned metals or tin-nickel alloys being applied to these metal materials from non-aqueous electrolytes of anhydrous metal compounds deposited and then then galvanically deposited aluminum in a manner known per se.
  • a layer thickness of 1 to 4 ⁇ m is generally sufficient to ensure adhesion between the material, intermediate layer and galvanoaluminium layer.
  • soluble anodes it is expedient to use those from the metal in question or, in the case of alloy deposition, those from the metals to be deposited or corresponding alloy anodes set.
  • the metal (II) compounds are expediently used; in the deposition of Cu one generally starts from Cu (I) compounds.
  • the anhydrous metal salts are preferably the anhydrous metal dichlorides or dibromides in the case of Fe, Co and Ni or copper (I) chloride or bromide or their addition compounds with alcohols, such as, for example, methanol or ethanol, or with ethers, such as, for example, diethyl ether, THF or dimethoxyethane , used.
  • concentrations of conductive salt, especially lithium bromide, should be of approximately the same to twice the order of magnitude.
  • the electrolysis temperatures are between room temperature and approx. 120 ° C. Temperatures between 50 and 80 ° C. are preferred. Good, uniform and shiny metal layers made of Fe, Co, Ni or Cu can be achieved with current densities between 0.2 and 1.5 A / dm 2 , 0.5 to 1.0 A / dm 2 are preferred, see Table 1.
  • alloy deposits mixtures of solutions of the metal salts of the alloy components are generally used according to the invention.
  • the anodes can then be either those made of appropriate alloys or a plurality of electrodes made of the metals of the individual alloy components. If there is a large electrolyte supply, it is possible to work only with the anode made from one of the alloy components. The concentration of the other alloy component must then be refreshed from time to time in the solution by adding the appropriate salt. If the deposition tendencies of the individual metals are very different, electrolytes containing only the salt of the more difficult to deposit metal can also be used when using alloy anodes.
  • the electrolyses are carried out in closed vessels in an inert gas atmosphere of e.g. Argon and / or nitrous oxide and / or nitrogen executed.
  • the workpieces are first washed with the solvent of the electrolyte. After the solvent has been drained off and dried in an inert gas stream or in vacuo, the workpieces are washed with dry toluene and then transferred to the aluminizing bath via an inert gas lock.
  • a particular advantage of such a procedure is that no new oxide or water layer can be formed on the metal surface. Furthermore, there is no need for subsequent, complex drying processes before entering the aluminizing bath, such as treatment with fluorocarbons containing wetting agents.
  • a cylindrical glass vessel with an edge ground flat at the top serves as the electrolysis cell and can be firmly closed with a lid made of insulating material.
  • a cathode made of the material to be coated for example WL-1.6359, is suspended from the lid between two anode plates made of the electrochemically dissolvable metal, for example nickel.
  • the attachments of the electrodes also serve as power supply.
  • the dry cell is filled with inert gas, such as argon or nitrogen.
  • a solution of 0.05 mol NiCt z 0.63 THF and 0.05 mol LiBr in 1 liter CH s OCH z CH z OH is used as the electrolyte to coat the cathode with nickel. Electrolysis is carried out at 60 ° C.
  • the anodic and cathodic current yields are quantitative in relation to the amount of current.
  • the workpieces are washed with the solvent of the electrolyte and dried in a stream of inert gas.
  • the workpieces are then washed with dry toluene and transferred to the aluminizing bath via an inert gas lock.
  • the "tape test” is a quantitative comparative method that enables liability assessments to be carried out in a simple manner.
  • an adhesive strip is first pressed firmly onto the galvanic layer and then quickly torn off. In the event of poor or moderate adhesion, the galvanic layer and the adhesive strip come off the material base. If the adhesion is good, only small areas of the electroplating layer are detached and if the adhesion is very good, the bonding of the electroplating layer to the base is completely preserved.

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Abstract

Processes are disclosed for the metal coating of metallic material, in particular of low-alloyed high-strength steels which are characterised in that electrodeposited adhesion promotion layers composed of iron, iron and nickel, nickel, cobalt, copper or alloys of the abovementioned metals or zinc/nickel alloys are deposited on said metallic materials from non-aqueous electrolytes and aluminium is then electrodeposited thereon in a manner known per se.

Description

Die Erfindung betrifft Verfahren zur Metallbeschichtung von Metallwerkstoffen, insbesondere von niedriglegierten, hochfesten Stählen.The invention relates to methods for the metal coating of metal materials, in particular of low-alloy, high-strength steels.

Die Erfindung betrifft außerdem die im Rahmen des obigen Verfahrens eingesetzten nichtwäßrigen Elektrolyte.The invention also relates to the non-aqueous electrolytes used in the above process.

Bestimmte Metalle, wie beispielsweise Kupfer, können nach entsprechenden mechanischen und/oder chemischen Vorbehandlungen zur Entfernung von Fett- und/oder Oxidschichten von der Oberfläche der Werkstücke direkt mit Aluminium haftfest galvanisch beschichtet werden. Auf anderen Metallen, wie beispielsweie Eisenwerkstoffen und insbesondere Spezialstählen, können im allgemeinen auf gleiche Weise keine haftfesten Schichten von Galvanoaluminium erhalten werden.Certain metals, such as copper, can be directly electroplated with aluminum after appropriate mechanical and / or chemical pretreatments to remove fat and / or oxide layers from the surface of the workpieces. On other metals, such as, for example, iron materials and in particular special steels, generally no adhesive layers of galvanoaluminium can be obtained in the same way.

Daher wurden verschiedene Verfahren zur Vorbereitung von Werkstücken aus elektrisch leitfähigen Materialien, inbesondere Metallen für eine haftfeste galvanische Beschichtung mit Aluminium, vorgeschlagen.Therefore, various methods for the preparation of workpieces made of electrically conductive materials, in particular metals for an adhesive galvanic coating with aluminum, have been proposed.

Die DE-PS 22 60 191 (Siemens AG, Priorität: 08.12.1972) beschreibt ein solches Verfahren, das dadurch gekennzeichnet ist, daß zumindest der letzte, der Formgebung der Werkstücke dienende Verfahrensschritt unter aprotischem wasser- und sauerstoff-freiem Schutzmedium durchgeführt wird. In den Beispielen wird als letzter der Formgebung dienender Verfahrensschritt Fräsen, Sägen oder Schmirgeln genannt.DE-PS 22 60 191 (Siemens AG, priority: 08.12.1972) describes such a method, which is characterized in that at least the last process step, which is used to shape the workpieces, is carried out under an aprotic, water- and oxygen-free protective medium. In the examples, milling, sawing or sanding are mentioned as the last shaping process step.

In der DE-OS 31 12 919 (Siemens AG, Priorität: 31.03.1981) wird vorgeschlagen, zur Haftvermittlung auf Eisenwerkstücken galvanisch aus wäßrigen Lösungen dünne Schichten aus Kobalt oder Kobaltlegierungen aufzubringen. Zur Haftvermittlung mit dem anschließend galvanisch aufzubringenden Aluminium sollen Schichtdicken von maximal 1 µm ausreichen.In DE-OS 31 12 919 (Siemens AG, priority: March 31, 1981) it is proposed to apply thin layers of cobalt or cobalt alloys galvanically from aqueous solutions to impart adhesion to iron workpieces. Layer thicknesses of a maximum of 1 µm should be sufficient to impart adhesion with the aluminum that is subsequently to be electroplated.

Bereits früher (H. Lehmkuhl, Dissertation, Technische Hochschule Aachen, 1954) wurde empfohlen, galvanisch aus wäßrigen Elektrolyten abgeschiedene Kupferschichten zur Haftvermittlung zwischen Eisenwerkstücken und galvanisch erzeugten Aluminiumschichten zu verwenden.Previously (H. Lehmkuhl, dissertation, Technical University of Aachen, 1954), it was recommended to use copper layers galvanically separated from aqueous electrolytes to promote adhesion between iron workpieces and galvanically produced aluminum layers.

Entscheidender Nachteil der beiden zuletzt genannten Verfahrensweisen ist, daß bei der galvanischen Abscheidung der als Haftvermittler dienenden Metalle aus wäßrigen Lösungen eine Mitabscheidung von Wasserstoff nicht zu vermeiden ist. Niedriglegierte hochfeste Stähle, wie beispielsweise in Tabelle 1 angegeben, sind jedoch sehr versprödungempfindlich gegenüber Wasserstoff. Wäßrige Elektrolytlösungen sind daher zur Beschichtung solcher Stähle ungeeignet.A decisive disadvantage of the two last-mentioned procedures is that during the electrodeposition of the metals serving as adhesion promoters, co-separation of hydrogen cannot be avoided. Low-alloy high-strength steels, for example as shown in Table 1, are very sensitive to embrittlement to hydrogen. Aqueous electrolyte solutions are therefore unsuitable for coating such steels.

Aus der DE-A-2012846 sind nicht wäßrige, DMSO enthaltende Lösungen von Metallsalzen zum Elektroplattieren ohne Wasserstoffbrüchigkeit bekannt.DE-A-2012846 discloses non-aqueous, DMSO-containing solutions of metal salts for electroplating without hydrogen fragility.

Die Erfindung betrifft folglich Verfahren zur Metallbeschichtung von Metallwerkstoffen, insbesondere niedriglegierten hochfesten Stählen, wobei aus nichtwäßrigen Elektrolyten wasserfreier Metallverbindungen galvanisch Haftvermittlungsschichten aus Eisen, Eisen und Nickel, Nickel, Cobalt, Kupfer oder Legierungen der vorstehend genannten Metalle oder Zinn-Nickel-Legierungen auf diese Metallwerkstoffe abgeschieden und darauf dann anschließend in an sich bekannter Weise galvanisch Aluminium abgeschieden wird.The invention consequently relates to methods for the metal coating of metal materials, in particular low-alloy high-strength steels, galvanic adhesion-promoting layers of iron, iron and nickel, nickel, cobalt, copper or alloys of the abovementioned metals or tin-nickel alloys being applied to these metal materials from non-aqueous electrolytes of anhydrous metal compounds deposited and then then galvanically deposited aluminum in a manner known per se.

Bei Verwendung dieser Metalle als Zwischenschichten für eine anschließende Aluminierung auf galvanischem Weg ist im allgemeinen eine Schichtdicke von 1 bis 4 µm ausreichend, um Haftung zwischen Werkstoff, Zwischenschicht und Galvanoaluminiumschicht zu gewährleisten.When using these metals as intermediate layers for a subsequent aluminizing by galvanic means, a layer thickness of 1 to 4 µm is generally sufficient to ensure adhesion between the material, intermediate layer and galvanoaluminium layer.

Als Elektrolyte werden, um die Abscheidung von Wasserstoff und die damit verbundene Gefahr der Versprödung der Werkstoffe zu vermeiden, Lösungen wasserfreier Metallsalze des Fe, Co, Ni, Cu oder Sn, insbesondere deren wasserfreie Halogenide und/oder die Komplexverbindungen dieser Metallhalogenide mit Ethern, wie beispielsweise Tetrahydrofuran, oder mit Alkoholen, wie beispielsweise Ethanol, in wasserfreien Alkylhalbethern eines C2-C3-Alkylenglykols der Formel

Figure imgb0001
in der

  • R für C1 bis C6 und Phenyl, und
  • R1 für H oder Methyl steht,

oder Mischungen dieser Lösungen unter Zusatz wasserfreier Leitsalze, insbesondere Lithiumchlorid, Lithiumbromid oder entsprechende Tetraorganylammoniumhalogenide verwendet.In order to avoid the deposition of hydrogen and the associated risk of embrittlement of the materials, electrolytes are solutions of anhydrous metal salts of Fe, Co, Ni, Cu or Sn, in particular their anhydrous halides and / or the complex compounds of these metal halides with ethers, such as for example tetrahydrofuran, or with alcohols, such as ethanol, in anhydrous alkyl half ethers of a C 2 -C 3 alkylene glycol of the formula
Figure imgb0001
 in the
  • R is C 1 to C 6 and phenyl, and
  • R 1 represents H or methyl,

or mixtures of these solutions with the addition of anhydrous conductive salts, in particular lithium chloride, lithium bromide or corresponding tetraorganylammonium halides.

Weiter werden als lösliche Anoden zweckmäßig solche aus dem betreffenden Metall oder bei derAbscheidung von Legierungen solche aus den abzuscheidenden Metallen oder entsprechende Legierungsanoden eingesetzt.Furthermore, as soluble anodes, it is expedient to use those from the metal in question or, in the case of alloy deposition, those from the metals to be deposited or corresponding alloy anodes set.

Bei Fe-, Co-, Ni- und Sn-Verbindungen werden zweckmäßig die Metall(II)-Verbindungen eingesetzt, bei der Abscheidung von Cu geht man im allgemeinen von Cu(I)-Verbindungen aus.In the case of Fe, Co, Ni and Sn compounds, the metal (II) compounds are expediently used; in the deposition of Cu one generally starts from Cu (I) compounds.

Die Verwendung von 2-Ethoxyethanol als Lösungsmittel von Elektrolyten zur Abscheidung von Cu, Ni, Co ist von A.L. Chaney, C.A. Mann, J. Phys. Chem 35 (1931) 2289 beschrieben worden. Im Gegensatz zum erfindungsgemäßen Verfahren wurden jedoch nur die Wasser enthaltenen Verbindungen (Cu(CI04 )22H20, Ni(Cl04)2 2H20 und Co(Cl04)2 2H20 beschrieben. Die Art der Metallabscheidung wird von den Autoren beim Cu als gut, beim Ni als weniger gut, weil spröde, und beim Co auch als weniger gut, weil schwarz, schwammig beschrieben. Ob diese Schichten als Haftvermittlungsschichten für Galvanoaluminium geeignet sind, ist nicht bekannt. Dies mußjedoch, insbesondere wegen der Eigenschaften der Ni- oder Co-Schichten, wie Sprödigkeit oder schwammiger Charakter, bezweifelt werden. Auf jeden Fall bleibt bei den durch die Metallsalze eingebrachten Wasseranteilen die Mitabscheidung von Wasserstoff unvermeidbar und damit verbunden die Gefahr der Versprödung der Werkstoffe durch Wasserstoff erhalten.The use of 2-ethoxyethanol as a solvent of electrolytes for the deposition of Cu, Ni, Co is from AL Chaney, CA Mann, J. Phys. Chem 35 (1931) 2289. In contrast to the method according to the invention, however, only the water-containing compounds (Cu (CI0 4 ) 2 2H 2 0, Ni (Cl0 4 ) 2 2H20 and Co (Cl0 4 ) 2 2H 2 0 have been described. The authors describe the type of metal deposition described as good for Cu, less good for Ni because it is brittle, and less good for Co because of its black, spongy nature. It is not known whether these layers are suitable as adhesion-promoting layers for galvanoaluminium Ni or Co layers, such as brittleness or spongy character, are doubted in any case. With the water components introduced by the metal salts, the co-separation of hydrogen remains unavoidable and the associated risk of embrittlement of the materials by hydrogen is maintained.

Die von A.J. Dill (Plating 1972, 59 (11), 1048-1052, Galvano-Organo 1974, 43, 151-156) beschriebene Abscheidung von Nickel aus Lösungen von NiCl2·6H20 in Ethylenglykol (1,2-Ethandiol) geht ebenfalls von einem wasserhaltigen Metallsalz aus. Die Mitabscheidung von Wasserstoff kann daher nicht vermieden werden. Ähnliches gilt für die von A.A. Sarabi, V.B. Singh, Indian J. of Technology 25 (1987) 119 untersuchte Nickelabscheidung aus 0.2 M Lösungen von NiCI2 nicht definierten Wassergehaltes oder NiS04.7 H20 in 1,2-Ethandiol oder 2-Methoxyethanol unter Zusatz von Borsäure (0.2 M). In 2-Methoxyethanol-NiCl2-H3B03-x H20-Elektrolyten sind die Nickelabscheidungen gleichmäßig, grauglänzend und haftend bei Stromdichten von 0.1-0.3 A/dm2, bei höheren Stromdichten zeigen sie eine Tendenz sich abzuschälen. Da die kathodischen Stromausbeuten nur 90-98 % betragen, muß angenommen werden, daß Wasserstoff mit abgeschieden wird. Hierzu ist allgemein bekannt (F.A. Cotton, G. Wilkinson, Anorganische Chemie, Verlag Chemie, Weinheim 1967, S. 245), daß Borsäure mit Alkoholen sehr leicht unter Abspaltung von Wasser Borsäureester bildet. Mit 1,2-Alkandiolen, wie 1,2-Ethandiol, entstehen stark saure Chelatkomplexe vom Typ

Figure imgb0002
The deposition of nickel from solutions of NiCl 2 .6H 2 0 in ethylene glycol (1,2-ethanediol) described by AJ Dill (Plating 1972, 59 (11), 1048-1052, Galvano-Organo 1974, 43, 151-156) also assumes a water-containing metal salt. The co-separation of hydrogen cannot therefore be avoided. The same applies to the nickel deposition investigated by AA Sarabi, VB Singh, Indian J. of Technology 25 (1987) 119 from 0.2 M solutions of NiCl 2 undefined water content or NiS0 4 .7 H 2 0 in 1,2-ethanediol or 2- Methoxyethanol with the addition of boric acid (0.2 M). In 2-methoxyethanol-NiCl 2 -H 3 B0 3 -x H 2 0 electrolytes, the nickel deposits are uniform, shiny gray and sticky at current densities of 0.1-0.3 A / dm 2 , at higher current densities they show a tendency to peel off. Since the cathodic current yields are only 90-98%, it must be assumed that hydrogen is also deposited. It is generally known (FA Cotton, G. Wilkinson, Inorganic Chemistry, Verlag Chemie, Weinheim 1967, p. 245) that boric acid forms very easily boric acid esters with the elimination of water with alcohols. With 1,2-alkanediols, such as 1,2-ethanediol, strongly acidic chelate complexes of the type are formed
Figure imgb0002

Beide Effekte verstärken die Gefahr der Wasserstoffabspaltung.Both effects increase the risk of hydrogen elimination.

Diese Gefahr besteht beim erfindungsgemäßen Verfahren nicht, da hier die wasserfreien Salze eingesetzt werden und das Lösungsmittel ebenfalls wasserfrei und ohne Zusatz von Säuren, insbesondere Borsäure, verwendet wird. Die anodischen und kathodischen Stromausbeuten sind bezogen auf aufgelöstes bzw. abgeschiedenes Metall quantitativ. Wasserstoff wird nicht abgeschieden. 1 Faraday, d.s. 26.8 Amperestunden, lösen anodisch 55.85/2 g Eisen, 58.94/2 g Kobalt oder 58.71/2 g Nickel entsprechend dem elektrolytischen Vorgang

Figure imgb0003
auf und scheiden kathodisch die gleichen Metallmengen entsprechend
Figure imgb0004
ab. Bei CuCI enthaltenden Elektrolytlösungen werden pro 1 Faraday 63.54 g Cu entsprechend
Figure imgb0005
aufgelöst und die gleiche Metallmenge entsprechend
Figure imgb0006
kathodisch abgeschieden. Als wasserfreie Metallsalze werden bevorzugt die wasserfreien Metalldichloride oder -dibromide bei Fe, Co und Ni bzw. Kupfer(I)chlorid oder -bromid oder deren Additionsverbindungen mit Alkoholen, wie beispielsweise Methanol oder Ethanol, oder mit Ethern, wie z.B. Diethylether, THF oder Dimethoxyethan, verwendet.This risk does not exist in the process according to the invention, since the anhydrous salts are used here and the solvent is also used anhydrous and without the addition of acids, in particular boric acid. The anodic and cathodic current yields are quantitative based on dissolved or deposited metal. Hydrogen is not separated out. 1 Faraday, ds 26.8 ampere-hours, anodically dissolve 55.85 / 2 g iron, 58.94 / 2 g cobalt or 58.71 / 2 g nickel according to the electrolytic process
Figure imgb0003
 on and cathodically separate the same amounts of metal accordingly
Figure imgb0004
 from. In the case of electrolytic solutions containing CuCI, 63.54 g of Cu per 1 Faraday are used
Figure imgb0005
 dissolved and the same amount of metal accordingly
Figure imgb0006
 deposited cathodically. The anhydrous metal salts are preferably the anhydrous metal dichlorides or dibromides in the case of Fe, Co and Ni or copper (I) chloride or bromide or their addition compounds with alcohols, such as, for example, methanol or ethanol, or with ethers, such as, for example, diethyl ether, THF or dimethoxyethane , used.

Als Lösungsmittel werden Alkylhalbether eines Alkylenglykols wie 1-Alkoxy-2-hydroxyethan oder 1-Alko- xy-2-hydroxypropan, insbesondere die leicht und preiswert zugänglichen Halbether des 1,2-Ethandiols ROCH2CH20H, bevorzugt solche mit R = Methyl, Ethyl, Propyl oder Isopropyl oder solche des 1,2-Propandiols, insbesondere CH3CH(OH)CH20CH3, eingesetzt.Alkyl half ethers of an alkylene glycol such as 1-alkoxy-2-hydroxyethane or 1-alkoxy-2-hydroxypropane, in particular the easily and inexpensively accessible half ethers of 1,2-ethanediol ROCH 2 CH 2 0H, preferably those with R = methyl, are used as solvents , Ethyl, propyl or isopropyl or those of 1,2-propanediol, in particular CH 3 CH (OH) CH 2 0CH 3 , used.

Als Metallsalzkonzentration in diesen Lösungsmitteln werden 0,02 bis 0,1 M, bevorzugt 0,044 bis 0,05 M Lösungen empfohlen. Die Konzentrationen an Leitsalz, insbesondere Lithiumbromid, sollten von etwa gleicher bis doppelter Größenordnung sein.0.02 to 0.1 M, preferably 0.044 to 0.05 M, solutions are recommended as the metal salt concentration in these solvents. The concentrations of conductive salt, especially lithium bromide, should be of approximately the same to twice the order of magnitude.

Die Elektrolysetemperaturen liegen zwischen Raumtemperatur und ca. 120°C bevorzugt werden Temperaturen zwischen 50 und 80 °C. Gute, gleichmäßige und glänzende Metallschichten aus Fe, Co, Ni oder Cu lassen sich mit Stromdichten zwischen 0,2 und 1,5 A/dm2 erreichen, bevorzugt werden 0,5 bis 1,0 A/dm2, siehe Tabelle 1.The electrolysis temperatures are between room temperature and approx. 120 ° C. Temperatures between 50 and 80 ° C. are preferred. Good, uniform and shiny metal layers made of Fe, Co, Ni or Cu can be achieved with current densities between 0.2 and 1.5 A / dm 2 , 0.5 to 1.0 A / dm 2 are preferred, see Table 1.

Bei Legierungsabscheidungen werden erfindungsgemäß im allgemeinen Mischungen aus Lösungen der Metallsalze der Legierungsbestandteile eingesetzt. Als Anoden können dann entweder solche aus entsprechenden Legierungen oder mehrere Elektroden aus den Metallen der einzelnen Legierungsbestandteile verwendet werden. Bei Vorhandensein eines größeren Elektrolytvorrats ist es möglich, nur mit der Anode aus einem der Legierungsbestandteile zu arbeiten. Die Konzentration des anderen Legierungsbestandteils muß dann in der Lösung durch Zugabe des entsprechenden Salzes von Zeit zu Zeit aufgefrischt werden. Wenn die Abscheidungstendenzen der Einzelmetalle sehr verschieden sind, lassen sich bei Verwendung von Legierungsanoden auch Elektrolyte verwenden, die nur das Salz des sich schwerer abscheidenden Metalls enthalten.In the case of alloy deposits, mixtures of solutions of the metal salts of the alloy components are generally used according to the invention. The anodes can then be either those made of appropriate alloys or a plurality of electrodes made of the metals of the individual alloy components. If there is a large electrolyte supply, it is possible to work only with the anode made from one of the alloy components. The concentration of the other alloy component must then be refreshed from time to time in the solution by adding the appropriate salt. If the deposition tendencies of the individual metals are very different, electrolytes containing only the salt of the more difficult to deposit metal can also be used when using alloy anodes.

Die Zusammensetzung der abzuscheidenden Legierung kann in weiten Bereichen variiert werden (siehe Tabelle 2) und zwar

  • 1. durch Veränderung des Verhältnisses der Metallsalze im Elektrolyten zueinander und/oder
  • 2. durch Verwendung von mehreren Anoden unterschiedlicher wirksamer Fläche aus den Metallen der einzelnen Legierungsbestandteile und/oder
  • 3. bei Einsatz mehrerer Anoden aus den Metallen der Legierungsbestandteile durch unterschiedliche Stromkreise zwischen der Kathode und den einzelnen Anoden.
The composition of the alloy to be deposited can be varied within a wide range (see Table 2)
  • 1. by changing the ratio of the metal salts in the electrolyte to one another and / or
  • 2. by using several anodes of different effective area from the metals of the individual alloy components and / or
  • 3. when using multiple anodes made of the metals of the alloy components through different circuits between the cathode and the individual anodes.

Um eine Luftoxidation der Metallsalzlösungen und/oder der galvanisch abgeschiedenen Metallschichten zu vermeiden, werden die Elektrolysen in geschlossenen Gefäßen in einer Inertgasatmosphäre von z.B. Argon und/oder Lachgas und/oder Stickstoff ausgeführt. Nach Beendigung der Zwischenbeschichtung werden die Werkstücke zunächst mit dem Lösungsmittel des Elektrolyten gewaschen. Nach Abtropfen des Lösungsmittels und Trocknen im Inertgasstrom oder im Vakuum werden die Werkstücke mit trockenem Toluol gewaschen und dann über eine Inertgasschleuse in das Aluminierbad überführt. Besonderer Vorteil einer solchen Verfahrensweise ist, daß auf der Metalloberfläche keine neue Oxid- oder Wasserschicht gebildet werden kann. Weiter entfallen nachträgliche aufwendige Trocknungsverfahren vor Eintritt in das Aluminierbad, wie beispielsweise die Behandlung mit Netzmittel enthaltenden Fluorkohlenwasserstoffen.In order to avoid air oxidation of the metal salt solutions and / or the electrodeposited metal layers, the electrolyses are carried out in closed vessels in an inert gas atmosphere of e.g. Argon and / or nitrous oxide and / or nitrogen executed. After finishing the intermediate coating, the workpieces are first washed with the solvent of the electrolyte. After the solvent has been drained off and dried in an inert gas stream or in vacuo, the workpieces are washed with dry toluene and then transferred to the aluminizing bath via an inert gas lock. A particular advantage of such a procedure is that no new oxide or water layer can be formed on the metal surface. Furthermore, there is no need for subsequent, complex drying processes before entering the aluminizing bath, such as treatment with fluorocarbons containing wetting agents.

Die Erfindung wird anhand der in den folgenden beiden Tabellen beschriebenen Ausführungsbeispiele erläutert.The invention is explained on the basis of the exemplary embodiments described in the following two tables.

Beispiel 1example 1

Als Elektrolysezelle dient ein zylindrisches Glasgefäß mit oben plan geschliffenem Rand, das mit einem Deckel aus isolierendem Material fest verschlossen werden kann. Am Deckel ist zwischen zwei Anodenplatten aus dem elektrochemisch aufzulösenden Metall, z.B. Nickel, eine Kathode aus dem zu beschichtenden Werkstoff, z.B. WL-1.6359 aufgehängt. Die Befestigungen der Elektroden dienen gleichzeitig als Stromzuführung. Die trockene Zelle wird mit Inertgas gefüllt, z.B. Argon oder Stickstoff. Zur Beschichtung der Kathode mit Nickel wird als Elektrolyt eine Lösung von 0.05 mol NiCtz 0.63 THF und 0.05 mol LiBr in 1 Liter CHsOCHzCHzOH eingesetzt. Es wird bei 60 °C mit einer Kathodenstromdichte von 0.5 A/dm2 bei ca. 3-4 Volt und guter Duchmischung des Elektrolyten solange elektrolysiert, bis sich eine 1 µ dicke Nickelschicht auf der Kathode abgeschieden hat. Bezogen auf die Strommenge sind die anodischen und kathodischen Stromausbeuten quantitativ.A cylindrical glass vessel with an edge ground flat at the top serves as the electrolysis cell and can be firmly closed with a lid made of insulating material. A cathode made of the material to be coated, for example WL-1.6359, is suspended from the lid between two anode plates made of the electrochemically dissolvable metal, for example nickel. The attachments of the electrodes also serve as power supply. The dry cell is filled with inert gas, such as argon or nitrogen. A solution of 0.05 mol NiCt z 0.63 THF and 0.05 mol LiBr in 1 liter CH s OCH z CH z OH is used as the electrolyte to coat the cathode with nickel. Electrolysis is carried out at 60 ° C. with a cathode current density of 0.5 A / dm 2 at approx. 3-4 volts and thorough mixing of the electrolyte until a 1 μm thick nickel layer has deposited on the cathode. The anodic and cathodic current yields are quantitative in relation to the amount of current.

In analoger Weise wurden andere, in Tabelle 1 aufgeführte Metallabscheidungen mit den in Tabelle 1 angegebenen Elektrolyten ausgeführt.

Figure imgb0007
In an analogous manner, other metal deposits listed in Table 1 were carried out with the electrolytes shown in Table 1.
Figure imgb0007

Beispiel 2Example 2

Dieses Beispiel beschreibt den in Tabelle 2 aufgeführten Versuch 1 detailliert. Eine 0.05 molare (M) Lösung von LiBr in CH30CH2CH2OH, die außerdem noch 0.029 M an NiCl2 und 0.015 M an FeCl2 ist, wird bei 65 °C in einer Inertgasatmosphäre mit einer Stromdichte von 0.5 A/dm2 elektrolysiert. Als Anoden werden Nickel- und Eisenblech verwendet; das Flächenverhältnis beider Metallanoden ist 1.0 : 0.5. Als Kathode wird ein Werkstück aus WL-1.7176 eingesetzt. Man elektrolysiert solange, bis sich auf der Kathode eine ca. 3 µ dicke Legierungsschicht abgeschieden hat. Die Legierung besteht zu 75 % aus Fe und zu 25 % aus Ni. Die Versuche 2-9 wurden analog mit den in Tabelle 2 angegebenen Elektrolyten und Anoden durchgeführt.This example describes Experiment 1 listed in Table 2 in detail. A 0.05 molar (M) solution of LiBr in CH 3 0CH 2 CH 2 OH, which is also 0.029 M in NiCl 2 and 0.015 M in FeCl 2 , is at 65 ° C in an inert gas atmosphere with a current density of 0.5 A / dm 2 electrolyzed. Nickel and iron sheets are used as anodes; the area ratio of both metal anodes is 1.0: 0.5. A workpiece made of WL-1.7176 is used as the cathode. Electrolysis is carried out until an approximately 3 μ thick alloy layer has been deposited on the cathode. The alloy consists of 75% Fe and 25% Ni. Experiments 2-9 were carried out analogously with the electrolytes and anodes shown in Table 2.

Nach derZwischenbeschichtung entsprechend den Beispielen 1 und 2 und den in Tabelle 1 und 2 zusaammengefaßten Versuchen werden die Werkstücke mit dem Lösungsmittel des Elektrolyten gewaschen und im Inertgasstrom getrocknet. Dann wäscht man die Werkstücke mit trockenem Toluol und überführt sie über eine Inertgasschleuse in das Aluminierbad.After the intermediate coating in accordance with Examples 1 and 2 and the experiments summarized in Tables 1 and 2, the workpieces are washed with the solvent of the electrolyte and dried in a stream of inert gas. The workpieces are then washed with dry toluene and transferred to the aluminizing bath via an inert gas lock.

Um ein quantitatives Maßfürdie Haftfestigkeit galvanisch erzeugter Schichten auf Werkstoffen zu erhalten, bedient man sich Verfahren zur Messung der Kraft, die benötigt wird, um den Niederschlag von der Unterlage abzureißen. Der "Tape-Test" ist eine quantitativ vergleichende Methode, die Bewertungen der Haftung auf einfache Weise ermöglicht. Dazu wird zunächst ein Klebestreifen fest auf die Galvanoschicht gepreßt und dann rasch abgerissen. Bei schlechter oder mäßiger Haftung löst sich dabei die Galvanoschicht zusammen mit dem Klebestreifen von der Werkstoffunterlage. Bei guter Haftung werden nur kleine Bezirke der Galvanoschicht abgelöst und bei sehr guter Haftung bleibt die Bindung der Galvanoschicht an die Unterlage vollständig erhalten.

Figure imgb0008
In order to obtain a quantitative measure of the adhesive strength of electroplated layers on materials, methods are used to measure the force that is required to tear the precipitate off the base. The "tape test" is a quantitative comparative method that enables liability assessments to be carried out in a simple manner. For this purpose, an adhesive strip is first pressed firmly onto the galvanic layer and then quickly torn off. In the event of poor or moderate adhesion, the galvanic layer and the adhesive strip come off the material base. If the adhesion is good, only small areas of the electroplating layer are detached and if the adhesion is very good, the bonding of the electroplating layer to the base is completely preserved.
Figure imgb0008

Claims (9)

1. A process for metal-plating of metallic materials, and more specifically low-alloy high-strength steels, wherein adhesion-bonding layers of iron, iron and nickel, nickel, cobalt, copper or alloys of said metals or tin- nickel alloys are electrodeposited on said metallic materials from non-aqueous electrolytes of anhydrous metal compounds, and then aluminium is electrodeposited thereon in a per se known manner.
2. The process according to claim 1, characterized in that as the anhydrous compounds there are employed metal salts of iron, cobalt, nickel, copper or tin, and more specifically of the anhydrous chlorides thereof and/or anhydrous bromides thereof and/or the complex compounds of the metal chlorides and/or metal bromides with ethers or with alcohols in water-free alkyl semi-ethers of a C2- to C3-alkylene glycol of the formula
Figure imgb0010
wherein
R represents Ci- to Cs-alkyl and phenyl, and
R1 represents a hydrogen atom or a methyl group,

or mixtures of these solutions with the addition of anhydrous supporting electrolytes, and more specifically lithium chloride, lithium bromide or respective tetraorganylammonium halides.
3. The process according to claim 2, characterized in that as the anhydrous metal compounds there are employed metal(II) compounds of iron, cobalt, nickel or tin or metal(l) compounds of copper.
4. The process according to claims 1 to 3, characterized in that as the anode a metal anode is used which has the same alloy composition as the metal cations of the metal salts of the electrolyte.
5. The process according to claims 1 to 4, characterized in that as the anhydrous solvent there is used a Ci- to C4-alkyl semi-ether, and preferably a C1- to C3-alkyl semi-ether, of an alkylene glycol, namely of 1,2-ethylene diol or of 1,2-propanediol.
6. The process according to claims 2 to 5, characterized in that in the solvent of the water-free electrolyte the metal salts are present in concentrations of from 0.02 to 0.1 M, and preferably of from 0.044 to 0.05M, and the supporting electrolyte, more particularly the lithium bromide, is present in an equimolar to twice the equimolar concentration relative to said metal salts.
7. The process according to claims 1 to 6, characterized in that the bonding layers are electrodeposited at current densities at from 0.2 to 1.5 A/dm2, and preferably at from 0.5 to 1.0 A/dm2, at electrolysis temperatures between room temperature (20 °C) and about 120 °C, and preferably between 50 °C and 80 °C.
8. The process according to claims 1 to 7, characterized in that the electrodeposition is effected in an inert gas atmosphere.
9. Non-aqueous electrolytes having the compositions as set forth in claims 2, 3, 5 and 6 for metal-plating of metallic materials, and more specifically low-alloy high-strength steels, and for adhesion-bonding between said metallic materials and aluminium layers electro-deposited thereon.
EP89102319A 1988-02-12 1989-02-10 Process concerning the adhesion between metallic materials and galvanic aluminium layers and the non-aqueous electrolyte used therein Expired - Lifetime EP0328128B2 (en)

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DE3804303 1988-02-11
DE3804303A DE3804303A1 (en) 1988-02-12 1988-02-12 METHOD FOR ADMINISTERING BETWEEN METAL MATERIALS AND GLAVAN ALUMINUM LAYERS AND NON-AQUE ELECTROLYTE USED THEREOF

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US8225481B2 (en) * 2003-05-19 2012-07-24 Pratt & Whitney Rocketdyne, Inc. Diffusion bonded composite material and method therefor
EP1524336A1 (en) * 2003-10-18 2005-04-20 Aluminal Oberflächtentechnik GmbH & Co. KG Workpieces coated with an aluminum magnesium alloy
DE102008048109B4 (en) * 2008-04-17 2015-01-29 Ks Aluminium-Technologie Gmbh Method for producing a metallic component and use of a cylinder part as basic body for carrying out the method
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