EP0084816B2 - Electrolyte for galvanic deposition of aluminium - Google Patents
Electrolyte for galvanic deposition of aluminium Download PDFInfo
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- EP0084816B2 EP0084816B2 EP83100245A EP83100245A EP0084816B2 EP 0084816 B2 EP0084816 B2 EP 0084816B2 EP 83100245 A EP83100245 A EP 83100245A EP 83100245 A EP83100245 A EP 83100245A EP 0084816 B2 EP0084816 B2 EP 0084816B2
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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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/42—Electroplating: Baths therefor from solutions of light metals
- C25D3/44—Aluminium
Definitions
- the invention relates to an organometallic electrolyte for the electrodeposition of aluminum and the use of this electrolyte.
- Organometallic electrolytes ie organoaluminum complex compounds (DE-PS 1 047 450 and dissertation H.Letruckiche, TH Hachen, 1954) can be used for the galvanic deposition of aluminum.
- organoaluminum complex compounds DE-PS 1 047 450 and dissertation H.Letruckiche, TH Hachen, 1954
- a large number of compounds have been described which can be used for galvanic aluminizing, for example onium and alkali complex compounds.
- the complex salt NaF.2 Al (C 2 H 5 ) 3 described as optimal has been used ("Zeitschrift für inorganic und Rheine Chemie", vol. 283, 1956, pp. 414 to 424).
- Electroplating baths with NaF.2 Al (C 2 H 5 ) 3 as electrolyte salt have a decisive disadvantage for a technically broad and economical application: the spreadability is too low. It is comparable to that of aqueous chrome baths ("Galvanotechnik", vol. 73, 1982, pp. 2 to 8). Due to the low spreadability in galvanic aluminizing, strongly profiled parts can only be coated as rack goods where the geometry of the parts allows, using auxiliary anodes. However, this is a technically very complex and therefore expensive process. Due to the low spreadability, the drum aluminizing of small parts was also of no practical importance, since the aluminized parts have too great variations in layer thickness or are not coated at all at critical points.
- the object of the invention is to provide an organometallic electrolyte for the electrodeposition of aluminum, which has a high scatterability but also a high conductivity and good solubility and is easily accessible commercially.
- Me means metal
- Et stands for an ethyl radical, ie for C 2 H 5 ; otherwise, different metals can also be present side by side.
- the organoaluminum electrolyte according to the invention according to formula (1) proves to be extremely advanced in terms of electroplating technology, ie it fulfills the requirements placed on electrolytes for a technically widely applicable and economical aluminizing process to a far greater extent than was previously possible.
- the electrolyte according to the invention namely has a high scattering capacity and, at the same time, the electrical conductivity and solubility required for economical aluminizing, as well as good commercial accessibility. For the first time, it combines the electrotechnical properties relevant to electroplating. Another advantage is also that this electrolyte compared to NaF. 2 Al (C 2 H 5 ) 3 has a significantly lower sensitivity to oxygen and moisture.
- the electrolyte according to the invention is based on findings which have been obtained on the one hand with regard to the relationships between the composition of organoaluminum complex compounds and the electroplating requirements, such as scatterability, conductivity and solubility (in low-viscosity aromatic hydrocarbons which are liquid at room temperature and have low water absorption). These relationships were previously unknown.
- the electrolyte according to the invention is comparable to cadmium electrolytes in terms of scatterability in the field of electro-technical interest. For the first time there is the possibility to aluminize the same product range as for cadming. This creates the electro-technical prerequisite for replacing cadmium with aluminum as a corrosion protection coating.
- the electrolyte according to the invention is preferably used in the form of a solution.
- Aromatic hydrocarbons which are liquid at room temperature, such as toluene, are advantageously used as solvents in the following composition: 1 mol of electrolyte salt per 1 to 10 mol, preferably 1 to 5 mol, of solvent.
- Approx. 1140 ml of toluene are placed in a Witt'schen stirring pot (capacity: 3 l), which is equipped with a mechanical stirrer, a dropping funnel, a thermometer and an inert gas transfer system and has a conductivity cell, and 183.5 g of potassium fluoride are slurried therein Slurry is gradually added with stirring, 577 g of aluminum triethyl and 250 g of aluminum triisobutyl.
- the electrolyte KF - [1.6 Al (C 2 H 5 ) 3 ⁇ 0.4Al (iC 4 H 9 ) 3 ] ⁇ 3.4 mol of toluene forms as clear, colorless, while increasing the specific conductivity and heating After the reaction liquid, this electrolyte composition - at 100 ° C - a specific conductivity of 2,25.10- 2 S ⁇ cm -1.
- the same method can also be used to produce electrolytes with a different composition.
- the solvent-free electrolytes can also be produced in this way. To do this, however, it is necessary to carry out the reaction above the melting temperature of the respective electrolyte.
- the good scatterability of the electrolyte according to the invention is to be demonstrated on the basis of electroplating tests.
- a galvanizing cell in the form of a rectangular glass vessel (20 cm x 8 cm x 20 cm) was used to carry out the electroplating tests, and an Al anode plate was attached to each end. Since the aluminum electrolytes to air and moisture sensitive, the plating was l elle with a special lid provided having a plurality of openings for a thermometer (diagonally opposite to a conductivity cell, for a gas transfer tube (for flooding the cell with nitrogen) for two stirrers in the corners of the cell in front of the anodes) and for charging the test specimens to be aluminized. Rectangular angle plates made of steel of a certain size were used as test specimens. To determine the scatterability, the thickness of the aluminum layer deposited on the angle plates was determined by means of a layer thickness measuring device
- test specimens were pretreated, as is customary in electroplating, ie pickled and degreased.
- the test specimen attached to a cathode rod was first degreased using an organic solvent and pickled by immersion in dilute hydrochloric acid.
- the test specimen was then degreased cathodically and an approximately 1 ⁇ m thick nickel layer was provided to improve the adhesive strength.
- the toluene-moist test specimen was introduced into the electroplating cell, ie into the electrolyte, and - as a cathode - arranged between the two anodes (cathode area: 2 dm 2 ; Distance between anode and cathode: approx. 10 cm each).
- the electroplating was carried out at an electrolyte temperature of 100 ° C by means of a so-called pulse current (deposition voltage: ⁇ 10 V).
- the test specimens were alternately poled cathodically and anodically, the cathodic deposition time in each case 80 ms and the anodic deposition time in each case 20 ms.
- electrolyte according to the invention the well-known electrolyte NaF.2 Al (C 2 H 5 ) 3 and, in each case in the commercially available form, a cadmium electrolyte (cyanidic), a zinc electrolyte (weakly cyanidic) and a nickel electrolyte (weakly acidic) were investigated, with the last three electrolytes were galvanized using direct current.
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Abstract
Description
Die Erfindung betrifft einen metallorganischen Elektrolyt zur galvanischen Abscheidung von Aluminium sowie die Verwendung dieses Elektrolyten.The invention relates to an organometallic electrolyte for the electrodeposition of aluminum and the use of this electrolyte.
Zur galvanischen Abscheidung von Aluminium können metallorganische Elektrolyte, d.h. aluminiumorganische Komplexverbindungen (DE-PS 1 047 450 und dissertation H.Letruckiche, TH Hachen, 1954), verwendet werden. In der Vergangenheit wurde eine Vielzahl von Verbindungen beschrieben, die für das galvanische Aluminieren in Frage kommen können, beispielsweise Onium-und Alkalikomplexverbindungen. In der Praxis wird bisher aber ausschliesslich das als optimal beschriebene Komplexsalz NaF.2 Al(C2H5)3 eingesetzt ("Zeitschrift für anorganische und allgemeine Chemie", Bd. 283, 1956, S. 414 bis 424).Organometallic electrolytes, ie organoaluminum complex compounds (DE-PS 1 047 450 and dissertation H.Letruckiche, TH Hachen, 1954) can be used for the galvanic deposition of aluminum. In the past, a large number of compounds have been described which can be used for galvanic aluminizing, for example onium and alkali complex compounds. In practice, however, only the complex salt NaF.2 Al (C 2 H 5 ) 3 described as optimal has been used ("Zeitschrift für inorganic und Allgemeine Chemie", vol. 283, 1956, pp. 414 to 424).
Galvanisierbäder mit NaF.2 Al(C2H5)3 als Elektrolytsalz haben für eine technisch breite und wirtschaftliche Anwendung jedoch einen entscheidenden Nachteil: die Streufähigkeit ist zu gering. Sie ist vergleichbar mit derjenigen von wässrigen Chrombädern ("Galvanotechnik", Bd. 73,1982, S. 2 bis 8). Aufgrund der geringen Streufähigkeit beim galvanischen Aluminieren können deshalb stark profilierte Teile als Gestellware, dort wo die Geometrie der Teile es gestattet, nur unter Verwendung von Hilfsanoden beschichtet werden. Dies ist aber ein technisch sehr aufwendiges und damit teures Verfahren. Aufgrund der geringen Streufähigkeit hat auch das Trommelaluminieren von Kleinteilen keine praktische Bedeutung erlangen können, da die aluminierten Teile zu grosse Schichtdickenschwankungen aufweisen bzw. an kritischen Stellen überhaupt nicht beschichtet sind.Electroplating baths with NaF.2 Al (C 2 H 5 ) 3 as electrolyte salt have a decisive disadvantage for a technically broad and economical application: the spreadability is too low. It is comparable to that of aqueous chrome baths ("Galvanotechnik", vol. 73, 1982, pp. 2 to 8). Due to the low spreadability in galvanic aluminizing, strongly profiled parts can only be coated as rack goods where the geometry of the parts allows, using auxiliary anodes. However, this is a technically very complex and therefore expensive process. Due to the low spreadability, the drum aluminizing of small parts was also of no practical importance, since the aluminized parts have too great variations in layer thickness or are not coated at all at critical points.
Aufgabe der Erfindung ist es, einen metallorganischen Elektrolyt zur galvanischen Abscheidung von Aluminium anzugeben, der eine hohe Streufähigkeit, aber auch eine hohe Leitfähigkeit und eine gute Löslichkeit aufweist und kommerziell leicht zugänglich ist.The object of the invention is to provide an organometallic electrolyte for the electrodeposition of aluminum, which has a high scatterability but also a high conductivity and good solubility and is easily accessible commercially.
Dies wird erfindungsgemäss durch einen Elektrolyt erreicht, der folgende Zusammensetzung aufweist:
- Me = K, Rb oder Cs;
- R = H oder CxH2x+1 mit x = 1 und 3 bis 8,
wovei wenigtens zwei Gruppen R Alkylreste sind; - m = 1,3 bis 2,4 und n = 0,2 bis 0,5.
- Me = K, Rb or Cs;
- R = H or C x H 2x + 1 with x = 1 and 3 to 8,
wovei at least two groups R are alkyl radicals; - m = 1.3 to 2.4 and n = 0.2 to 0.5.
In der vorstehenden Formel (1) bedeutet « Me » Metall, « Et steht für einen Äthylrest, d.h. für C2H5; im übrigen können auch verschiedene Metalle nebeneinander vorliegen.In the above formula (1), “Me” means metal, “Et stands for an ethyl radical, ie for C 2 H 5 ; otherwise, different metals can also be present side by side.
Vorteilhafte Ausgestaltungen des erfindungsgemässen Elektrolyten sind Gegenstand von Unteranspruchen, wobei ein Elektrolyt folgender Zusammensetzung besonders bevorzugt wird:
- m' = 1,8 bis 2,2 (insbesondere 2,0),
- n' = 0,2 bis 0,5 (insbesondere 0,4) und
- R' = CH3 oder C4H9, wobei die Reste R' n- oder iso-Butylreste sein können.
- m '= 1.8 to 2.2 (in particular 2.0),
- n '= 0.2 to 0.5 (in particular 0.4) and
- R '= CH 3 or C 4 H 9 , where the radicals R' can be n- or iso-butyl radicals.
Der erfindungsgemässe aluminiumorganische Elektrolyt gemäss Formel (1) erweist sich in galvanotechnischer Hinsicht als überaus fortschrittlich, d.h. er erfüllt die Forderungen, die an Elektrolyte für ein technisch breit anwendbares und wirtschaftliches Aluminierverfahren gestellt werden, in weit höherem Masse als dies bislangmöglich war. Der erfindungsgemässe Elektrolyt weist nämlich eine hohe Streufähigkeit bei gleichzeitig fürein wirtschaftliches Aluminieren erforderlicher elektrischer Leitfähigkeit und Löslichkeit sowie eine gute kommerzielle Zugänglichkeit auf. Er vereinigt in sich erstmals die galvanotechnisch relevanten Elektrolyteigenschaften. Ein weiterer Vorteil ist ferner auch, dass dieser Elektrolyt im Vergleich zu NaF. 2 Al(C2H5)3 eine wesentlich geringere Sauerstoff und Feuchtigkeitsempfindlichkeit besitzt.The organoaluminum electrolyte according to the invention according to formula (1) proves to be extremely advanced in terms of electroplating technology, ie it fulfills the requirements placed on electrolytes for a technically widely applicable and economical aluminizing process to a far greater extent than was previously possible. The electrolyte according to the invention namely has a high scattering capacity and, at the same time, the electrical conductivity and solubility required for economical aluminizing, as well as good commercial accessibility. For the first time, it combines the electrotechnical properties relevant to electroplating. Another advantage is also that this electrolyte compared to NaF. 2 Al (C 2 H 5 ) 3 has a significantly lower sensitivity to oxygen and moisture.
Der erfindungsgemässe Elektrolyt beruht auf Erkenntnissen, welche bezüglich der Zusammenhänge zwischen der Zusammensetzung aluminiumorganischer Komplexverbindungen einerseits und den galvanotechnischen Erfordernissen, wie Streufähigkeit, Leitfähigkeit und Löslichkeit (in bei Raumtemperatur flüssigen, niederviskosen aromatischen Kohlenwasserstoffen mit geringer Wasseraufnahme), andererseits gewonnen wurden. Diese Zusammenhänge waren bislang nicht bekannt.The electrolyte according to the invention is based on findings which have been obtained on the one hand with regard to the relationships between the composition of organoaluminum complex compounds and the electroplating requirements, such as scatterability, conductivity and solubility (in low-viscosity aromatic hydrocarbons which are liquid at room temperature and have low water absorption). These relationships were previously unknown.
Es hat sich nun gezeigt, dass für die Streufähigkeit das Metallion entscheidend ist, wohingegen die Lebtfähigkeit sowohl vom Metallion als auch vom Halogenion und von der Länge der Alkylreste beeinflusst wird. Für die Löslichkeit wiederum erweisen sich die Alkylreste und das Metallion als besonders relevantIt has now been shown that the metal is crucial for the Streuf similar ability, whereas the Lives ability is influenced by both the metal ion and the halogen ion and the length of the alkyl groups. The alkyl residues and the metal ion turn out to be particularly relevant for solubility
Im einzelnen gilt folgendes. Streufähigkeit, Leitfähigkeit und technische Handhabbarkeit des Elektrolyten werden mit steigendem lonenradius des Alkalimetalls verbessert, während sich beim Halogenion ein gegenläufiger Effekt ergibt Für eine hohe Leitfähigkeit sollen die Alkylreste wenig raumerfüllend und kurzkettig sein. Zur Erzielung einer guten Löslichkeit eignen sich kleine Metallionen besser als grosse.The following applies in detail. Scatterability, conductivity and technical handling of the electrolyte are improved with increasing ionic radius of the alkali metal, while the halogen ion has an opposing effect. Small metal ions are better suited than large ones to achieve good solubility.
Mit dem erfindungsgemässen Elektrolyt wurde erstmals ein technisch brauchbares Produkt geschaffen. Dies gilt insbesondere auch für die technische Handhabbarkeit, d.h. dieser Elektrolyt ist bei Raumtemperatur löslich und kann im galvanotechnisch interessanten Elektrolytkonzentrationsbereich in einfacher Weise transportiert werden.With the electrolyte according to the invention, a technically usable product was created for the first time. This also applies in particular to technical handling, ie this electrolyte is soluble at room temperature and can be transported in a simple manner in the electrolyte concentration range which is of interest in terms of electrotechnology.
Der erfindungsgemässe Elektrolyt ist - im galvanotechnisch interessanten Arbeitsbereich - hinsichtlich der Streufähigkeit mit Cadmiumelektrolyten vergleichbar. Damit ergibt sich erstmals die Möglichkeit, die gleiche Produktpalette wie beim Cadmieren zu aluminieren. Dadurch ist die galvanotechnische Voraussetzung geschaffen, um Cadmium als Korrosionsschutzüberzug durch Aluminium zu ersetzen.The electrolyte according to the invention is comparable to cadmium electrolytes in terms of scatterability in the field of electro-technical interest. For the first time there is the possibility to aluminize the same product range as for cadming. This creates the electro-technical prerequisite for replacing cadmium with aluminum as a corrosion protection coating.
Der erfindungsgemässe Elektrolyt wird vorzugsweise in Form einer Lösung eingesetzt. Als Lösungsmittel dienen insbesondere bei Raumtemperaturflüssige aromatische Kohlenwasserstoffe, wie Toluol, vorteilhaft in folgender Zusammensetzung: 1 Mol Elektrolytsalz pro 1 bis 10 Mol, vorzugsweise 1 bis 5 Mol, Lösungsmittel.The electrolyte according to the invention is preferably used in the form of a solution. Aromatic hydrocarbons which are liquid at room temperature, such as toluene, are advantageously used as solvents in the following composition: 1 mol of electrolyte salt per 1 to 10 mol, preferably 1 to 5 mol, of solvent.
Anhand von Beispielen soll die Erfindung noch näher erläutert werden.The invention will be explained in more detail with the aid of examples.
In einen Witt'schen Rührtopf (Fassungsvermögen: 3 I), der mit einem mechanischen Rührer, einem Tropftrichter, einem Thermometer und einem Inertgasüberleitungssystem versehen ist und eine Leitfähigkeitszelle aufweist, werden ca. 1140 ml Toluol gegeben und darin 183,5 g Kaliumfluorid aufgeschlämmt Dieser Aufschlämmung werden unter Rühren nach und nach 577 g Aluminiumtriäthyl und 250 g Aluminiumtriisobutyl zugesetzt. Dabei bildet sich, unter Ansteigen der spezifischen Leitfähigkeit und unter Erwärmung, der Elektrolyt KF - [1,6 Al(C2H5)3 · 0,4Al(iC4H9)3] · 3,4 mol Toluol als klare farblose Flüssigkeit Nach beendeter Umsetzung weist diese Elektrolytzusammensetzung - bei 100°C - eine spezifische Leitfähigkeit von 2,25.10-2 S·cm-1 auf.Approx. 1140 ml of toluene are placed in a Witt'schen stirring pot (capacity: 3 l), which is equipped with a mechanical stirrer, a dropping funnel, a thermometer and an inert gas transfer system and has a conductivity cell, and 183.5 g of potassium fluoride are slurried therein Slurry is gradually added with stirring, 577 g of aluminum triethyl and 250 g of aluminum triisobutyl. The electrolyte KF - [1.6 Al (C 2 H 5 ) 3 · 0.4Al (iC 4 H 9 ) 3 ] · 3.4 mol of toluene forms as clear, colorless, while increasing the specific conductivity and heating After the reaction liquid, this electrolyte composition - at 100 ° C - a specific conductivity of 2,25.10- 2 S · cm -1.
Nach derselben Methode können auch Elektrolyte mit anderer Zusammensetzung hergestellt werden. Ebenso lassen sich auf diese Weise prinzipiell auch die lösungsmittelfreien Elektrolyte herstellen. Hierzu ist es allerdings erforderlich, die Reaktion oberhalb der Schmelztemperatur des jeweiligen Elektrolyten durchzuführen.The same method can also be used to produce electrolytes with a different composition. In principle, the solvent-free electrolytes can also be produced in this way. To do this, however, it is necessary to carry out the reaction above the melting temperature of the respective electrolyte.
In der nachfolgenden Tabelle ist die elektrische Leitfähigkeit (in 10-2 S·cm-1) bei 100°C für mehrere Elektrolyte der allgemeinen Form KF.[(2-n) AlEt3· n AIR3] · 3,4 mol Toluol angegeben.
Anhand von Galvanisierversuchen soll die gute Streufähigkeit des erfindungsgemässen Elektrolyten aufgezeigt werden. Zur Durchführung der Galvanisierversuche diente eine Galvanisierzelle in Form eines rechteckigen Glasgefässes (20 cm x 8 cm x 20 cm), an dessen Stirnseiten je ein Al- Anodenblech angebracht war. Da die Aluminiumelektrolyte luft- und feuchtigkeitsempfindlich sind, wurde die Galvanisierlelle mit einem speziellen Deckel versehen, der mehrere Öffnungen aufweist für ein Thermometer, für eine Leitfähigkeitszelle, für ein Gasüberleitungsrohr (zum Fluten der Zelle mit Stickstoff), für zwei Rührer (diagonal gegenüberstehend in den Ecken der Zelle vor den Anoden befindlich) und zum Chargieren der zu aluminierenden Prüfkörper. Als Prüfkörper dienten Rechteck-Winkelbleche aus Stahl bestimmter Grösse. Zur Ermittlung der Streufähigkeit wurde die Dicke der auf den Winkelblechen abgeschiedenen Aluminiumschicht mittels eines Schichtdickenmessgerätes bestimmtThe good scatterability of the electrolyte according to the invention is to be demonstrated on the basis of electroplating tests. A galvanizing cell in the form of a rectangular glass vessel (20 cm x 8 cm x 20 cm) was used to carry out the electroplating tests, and an Al anode plate was attached to each end. Since the aluminum electrolytes to air and moisture sensitive, the plating was l elle with a special lid provided having a plurality of openings for a thermometer (diagonally opposite to a conductivity cell, for a gas transfer tube (for flooding the cell with nitrogen) for two stirrers in the corners of the cell in front of the anodes) and for charging the test specimens to be aluminized. Rectangular angle plates made of steel of a certain size were used as test specimens. To determine the scatterability, the thickness of the aluminum layer deposited on the angle plates was determined by means of a layer thickness measuring device
Vor dem Aluminieren wurden die einzelen Prüfkörper, wie in der Galvanik üblich, vorbehandelt, d.h. gebeizt und entfettet Dazu wurde jeweils der an einer Kathodenstange befestigte Prüfkörper zunächst mittels eines organischen Lösungsmittels vorentfettet und durch Tauchen in verdünnte Salzsäure gebeizt. Anschliessend wurde der Prüfkörper kathodisch entfettet und zur Haftfestigkeitsverbesserung mit einer ca. 1 µm dicken Nickelschichtversehen. Nach Spülen mitWasserund nachfolgender Entfernung des anhaftenden Wasserfilmes (mittels eines Entwässerungsmittels und durch anschliessendes Tauchen in Toluol) wurde der toluolfeuchte Prüfkörper in die Galvanisierzelle, d.h. in den Elektrolyt, eingebracht und - als Kathode - zwischen den beiden Anoden angeordnet (Kathodenfläche: 2 dm2; Abstand zwischen Anode und Kathode:jeweils ca 10 cm).Before the aluminizing, the individual test specimens were pretreated, as is customary in electroplating, ie pickled and degreased. For this purpose, the test specimen attached to a cathode rod was first degreased using an organic solvent and pickled by immersion in dilute hydrochloric acid. The test specimen was then degreased cathodically and an approximately 1 μm thick nickel layer was provided to improve the adhesive strength. After rinsing with water and subsequent removal of the adhering water film (using a dewatering agent and then immersing in toluene), the toluene-moist test specimen was introduced into the electroplating cell, ie into the electrolyte, and - as a cathode - arranged between the two anodes (cathode area: 2 dm 2 ; Distance between anode and cathode: approx. 10 cm each).
Die Galvanisierung erfolgte bei einer Elektrolyttemperatur von 100°C mittels eines sogenannten Impulsstromes (Abscheidungsspannung: ±10 V). Dazu wurden die Prüfkörper abwechselnd kathodisch und anodisch gepolt, wobei die kathodische Abscheidungszeit jeweils 80 ms und die anodische Abscheidungszeit jeweils 20 ms betrug.The electroplating was carried out at an electrolyte temperature of 100 ° C by means of a so-called pulse current (deposition voltage: ± 10 V). For this purpose, the test specimens were alternately poled cathodically and anodically, the cathodic deposition time in each case 80 ms and the anodic deposition time in each case 20 ms.
Zur Untersuchung gelangte neben dem erfindungsgemässen Elektrolyt der bekannte Elektrolyt NaF · 2 Al(C2H5)3 sowie, jeweils in handelsüblicher Form, ein Cadmiumelektrolyt (cyanidisch), ein Zinkelektrolyt (schwach cyanidisch) und ein Nickelelektrolyt (schwach sauer), wobei bei den drei letztgenannten Elektrolyten mittels Gleichstrom galvanisiert wurde. Dabei ergab sich folgendes: Beim Galvanisieren im normalen Arbeitsbereich (AI-Elektrolyte: 1 A/dm2; Cd-, Zn- und Ni-Elektrolyt: 2 A/dm2), unter sonst gleichen Bedingungen, beträgt beim bekannten Elektrolyt - in Form von NaF-2 AI(C2H5)3·3,4 mol Toluol -die Streufähigkeit lediglich ca. 13%, während der erfindungsgemässe Elektrolyt - in Form von KF. [1,6 Al(C2H5)3·0,4 Al(i-C4H9)3] · 3,4 mol Toluol - eine Streufähigkeit von ca. 38% aufweist, d.h. nahezu das Dreifache. Im Vergleich dazu beträgt die Streufähigkeit beim Zn-Elektrolyt ca. 30%, beim Ni-Elektrolyt ca. 33% und beim Cd-Elektrolyt ca. 40%.In addition to the electrolyte according to the invention, the well-known electrolyte NaF.2 Al (C 2 H 5 ) 3 and, in each case in the commercially available form, a cadmium electrolyte (cyanidic), a zinc electrolyte (weakly cyanidic) and a nickel electrolyte (weakly acidic) were investigated, with the last three electrolytes were galvanized using direct current. This resulted in the following: When electroplating in the normal working range (Al electrolytes: 1 A / dm 2 ; Cd, Zn and Ni electrolyte: 2 A / dm 2 ), under otherwise identical conditions, the known electrolyte is in shape of NaF-2 Al (C 2 H 5 ) 3 · 3.4 mol of toluene — the scatterability only about 13%, while the electrolyte according to the invention - in the form of KF. [1.6 Al (C 2 H 5 ) 3 · 0.4 Al (iC 4 H 9 ) 3 ] · 3.4 mol toluene - has a scattering capacity of approx. 38%, ie almost three times. In comparison, the scattering capacity is approximately 30% for the Zn electrolyte, approximately 33% for the Ni electrolyte and approximately 40% for the Cd electrolyte.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT83100245T ATE20252T1 (en) | 1982-01-25 | 1983-01-13 | ELECTROLYTE FOR ELECTROPLATING ALUMINUM. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3202265 | 1982-01-25 | ||
| DE19823202265 DE3202265A1 (en) | 1982-01-25 | 1982-01-25 | ELECTROLYTE FOR GALVANIC DEPOSITION OF ALUMINUM |
Publications (4)
| Publication Number | Publication Date |
|---|---|
| EP0084816A2 EP0084816A2 (en) | 1983-08-03 |
| EP0084816A3 EP0084816A3 (en) | 1984-06-06 |
| EP0084816B1 EP0084816B1 (en) | 1986-06-04 |
| EP0084816B2 true EP0084816B2 (en) | 1991-10-30 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP83100245A Expired - Lifetime EP0084816B2 (en) | 1982-01-25 | 1983-01-13 | Electrolyte for galvanic deposition of aluminium |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4417954A (en) |
| EP (1) | EP0084816B2 (en) |
| JP (1) | JPS58171591A (en) |
| AT (1) | ATE20252T1 (en) |
| CA (1) | CA1209157A (en) |
| DE (2) | DE3202265A1 (en) |
| DK (1) | DK154657C (en) |
| ES (1) | ES519248A0 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007018489A1 (en) | 2007-04-19 | 2008-10-23 | Tec-Chem Gmbh | Aluminum-organic four-component electrolyte for separating out aluminum consists of mixture of KF complexes, AIR13 and aromatic hydrocarbon |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4517253A (en) * | 1984-01-23 | 1985-05-14 | Rose Robert M | Cryoelectrodeposition |
| NL8602856A (en) * | 1986-11-11 | 1988-06-01 | Hga Galvano Aluminium B V | METHOD AND APPARATUS FOR GALVANIC SEPARATION OF METALS ON A SUBSTRATE |
| US4778575A (en) * | 1988-01-21 | 1988-10-18 | The United States Of America As Represented By The United States Department Of Energy | Electrodeposition of magnesium and magnesium/aluminum alloys |
| DE3919068A1 (en) * | 1989-06-10 | 1990-12-13 | Studiengesellschaft Kohle Mbh | ALUMINUM ORGANIC ELECTROLYTE FOR THE ELECTROLYTIC DEPOSITION OF HIGH-PURITY ALUMINUM |
| DE3919069A1 (en) * | 1989-06-10 | 1990-12-13 | Studiengesellschaft Kohle Mbh | ALUMINUM ORGANIC ELECTROLYTE AND METHOD FOR ELECTROLYTICALLY DEPOSITING ALUMINUM |
| EP0504705A1 (en) * | 1991-03-20 | 1992-09-23 | Siemens Aktiengesellschaft | Pretreatment of metallic material for the electrodeposition coating with metal |
| EP0504704A1 (en) * | 1991-03-20 | 1992-09-23 | Siemens Aktiengesellschaft | Pretreatment of metallic material for the electrodeposition coating with metal |
| EP0505886A1 (en) * | 1991-03-28 | 1992-09-30 | Siemens Aktiengesellschaft | Manufacture of decorative aluminium coatings |
| DE19649000C1 (en) * | 1996-11-27 | 1998-08-13 | Alcotec Beschichtungsanlagen G | Electrolyte for the electrodeposition of aluminum and its use |
| DE19716493C2 (en) * | 1997-04-19 | 2001-11-29 | Aluminal Oberflaechentechnik | Process for the electrolytic coating of metallic or non-metallic continuous products and device for carrying out the process |
| DE19716495C1 (en) * | 1997-04-19 | 1998-05-20 | Aluminal Oberflaechentechnik | Electrolyte for high speed electrolytic deposition of aluminium@ |
| US7250102B2 (en) * | 2002-04-30 | 2007-07-31 | Alumiplate Incorporated | Aluminium electroplating formulations |
| WO2002088434A1 (en) * | 2001-04-30 | 2002-11-07 | Alumiplate Incorporated | Aluminium electroplating formulations |
| DE10224089A1 (en) * | 2002-05-31 | 2003-12-11 | Studiengesellschaft Kohle Mbh | Process for the preparation of organo-aluminum complexes and their use for the production of electrolyte solutions for the electrochemical deposition of aluminum-magnesium alloys |
| EP1927680A1 (en) * | 2006-11-29 | 2008-06-04 | Aluminal Oberflächentechnik GmbH & Co. KG | Electrolyte for galvanic deposition of aluminium from aprotic solvents in a galvanising drum |
| US20120006688A1 (en) | 2009-03-18 | 2012-01-12 | Basf Se | Electrolyte and surface-active additives for the electrochemical deposition of smooth, dense aluminum layers from ionic liquids |
| US10190640B2 (en) | 2016-03-23 | 2019-01-29 | Schaeffler Technologies AG & Co. KG | Bearing with integrated shunt |
| US10794427B2 (en) | 2016-04-05 | 2020-10-06 | Schaeffler Technologies AG & Co. KG | Bearing ring with insulating coating |
| US10539178B2 (en) | 2017-05-18 | 2020-01-21 | Schaeffler Technologies AG & Co. KG | Vapor deposition bearing coating |
| US11142841B2 (en) | 2019-09-17 | 2021-10-12 | Consolidated Nuclear Security, LLC | Methods for electropolishing and coating aluminum on air and/or moisture sensitive substrates |
| US11661665B2 (en) | 2020-04-30 | 2023-05-30 | The Boeing Company | Aluminum and aluminum alloy electroplated coatings |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE540052A (en) * | 1955-06-13 | |||
| US4101386A (en) * | 1971-05-07 | 1978-07-18 | Siemens Aktiengesellschaft | Methods of coating and surface finishing articles made of metals and their alloys |
| US3929611A (en) * | 1974-07-19 | 1975-12-30 | Ametek Inc | Electrodepositing of aluminum |
| NL8100569A (en) * | 1981-02-06 | 1982-09-01 | Philips Nv | ELECTROLYLIC LIQUID FOR GALVANIC DEPOSITION OF ALUMINUM. |
-
1982
- 1982-01-25 DE DE19823202265 patent/DE3202265A1/en not_active Withdrawn
-
1983
- 1983-01-13 EP EP83100245A patent/EP0084816B2/en not_active Expired - Lifetime
- 1983-01-13 AT AT83100245T patent/ATE20252T1/en not_active IP Right Cessation
- 1983-01-13 DE DE8383100245T patent/DE3363841D1/en not_active Expired
- 1983-01-18 JP JP58006551A patent/JPS58171591A/en active Granted
- 1983-01-24 DK DK025183A patent/DK154657C/en not_active IP Right Cessation
- 1983-01-24 CA CA000420127A patent/CA1209157A/en not_active Expired
- 1983-01-25 US US06/460,817 patent/US4417954A/en not_active Expired - Lifetime
- 1983-01-25 ES ES519248A patent/ES519248A0/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007018489A1 (en) | 2007-04-19 | 2008-10-23 | Tec-Chem Gmbh | Aluminum-organic four-component electrolyte for separating out aluminum consists of mixture of KF complexes, AIR13 and aromatic hydrocarbon |
Also Published As
| Publication number | Publication date |
|---|---|
| DK25183D0 (en) | 1983-01-24 |
| US4417954A (en) | 1983-11-29 |
| JPS6122038B2 (en) | 1986-05-29 |
| ES8403490A1 (en) | 1984-03-16 |
| DK154657C (en) | 1989-05-01 |
| ES519248A0 (en) | 1984-03-16 |
| JPS58171591A (en) | 1983-10-08 |
| EP0084816A3 (en) | 1984-06-06 |
| EP0084816B1 (en) | 1986-06-04 |
| DK154657B (en) | 1988-12-05 |
| DE3363841D1 (en) | 1986-07-10 |
| EP0084816A2 (en) | 1983-08-03 |
| DK25183A (en) | 1983-07-26 |
| ATE20252T1 (en) | 1986-06-15 |
| DE3202265A1 (en) | 1983-07-28 |
| CA1209157A (en) | 1986-08-05 |
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